Pyridazine Compound and Use Thereof

ABSTRACT

A pyridazine compound represented by formula (1): 
                         
has an excellent plant disease controlling effect.

TECHNICAL FIELD

The present invention relates to a pyridazine compound, use thereof andits production intermediate.

BACKGROUND ART

Conventionally, agricultural fungicides have been developed, and a lotof compounds having a fungicidal activity have been found. However, aplant disease controlling effect of these compound's is not necessarilysufficient, and novel compounds having a plant disease controllingeffect are searched.

DISCLOSURE OF THE INVENTION

The present inventors have intensively studied to find a compound havingan excellent plant disease controlling effect, and resultantly foundthat a pyridazine compound represented by the following formula (1) hasan excellent plant disease controlling activity, completing the presentinvention.

That is, the present invention is as described in the following items 1to 7.

-   1. A pyridazine compound represented by formula (1) (referred as the    compound of the present invention, hereinafter):

wherein,R¹ represents a chlorine atom, a bromine atom or a C1-C4 alkoxy group;R² represents a C1-C4 alkyl group;R³ represents a halogen atom, a nitro group, a cyano group, a C1-C4alkyl group optionally substituted by at least one halogen atom, a C1-C4alkoxy group optionally substituted by at least one halogen atom or aC1-C4 alkylthio group optionally substituted by at least one halogenatom;m represents an integer of 0 to 5; provided that, when m represents aninteger of 2 or more, each of R³s is same or different;R⁴ represents a halogen atom, a nitro group, a cyano group, a C1-C4alkyl group optionally substituted by at least one halogen atom or aC1-C4 alkoxy group optionally substituted by at least one halogen atom;R⁵ represents a halogen atom, a nitro group, a cyano group, a C1-C4alkyl group optionally substituted by at least one halogen atom or aC1-C4 alkoxy group optionally substituted by at least one halogen atom;n represents an integer of 0 to 4; provided that, when n represents aninteger of 2 or more, each of R⁵s is same or different.2. A fungicidal composition comprising the compound of the presentinvention as an active ingredient.3. A method for controlling plant diseases comprising a step applying aneffective amount of the compound of the present invention to plants orsoils growing the plants.4. Use of the compound of the present invention as an active ingredientof a fungicidal composition.5. A compound represented by formula (2):

wherein,R² represents a C1-C4 alkyl group;R³ represents a halogen atom, a nitro group, a cyano group, a C1-C4alkyl group optionally substituted by at least one halogen atom, a C1-C4alkoxy group optionally substituted by at least one halogen atom or aC1-C4 alkylthio group optionally substituted by at least one halogenatom;m represents an integer of 0 to 5; provided that, when m represents aninteger of 2 or more, each of R³s is same or different;R⁴ represents a halogen atom, a nitro group, a cyano group, a C1-C4alkyl group optionally substituted by at least one halogen atom or aC1-C4 alkoxy group optionally substituted by at least one halogen atom;R⁵ represents a halogen atom, a nitro group, a cyano group, a C1-C4alkyl group optionally substituted by at least one halogen atom or aC1-C4 alkoxy group optionally substituted by at least one halogen atom;n represents an integer of 0 to 4; provided that, when n represents aninteger of 2 or more, each of R⁵s is same or different.6. A compound represented by formula (1-3):

wherein,R¹ represents a chlorine atom, a bromine atom or a C1-C4 alkoxy group;R² represents a C1-C4 alkyl group;R³⁻¹ represents a halogen atom, a cyano group, a C1-C4 alkyl groupoptionally substituted by at least one halogen atom, a C1-C4 alkoxygroup optionally substituted by at least one halogen atom or a C1-C4alkylthio group optionally substituted by at least one halogen atom;m represents an integer of 0 to 5; provided that, when m represents aninteger of 2 or more, each of R³⁻¹s is same or different.7. A compound represented by formula (3):

wherein,R² represents a C1-C4 alkyl group;R³ represents a halogen atom, a nitro group, a cyano group, a C1-C4alkyl group optionally substituted by at least one halogen atom, a C1-C4alkoxy group optionally substituted by at least one halogen atom or aC1-C4 alkylthio group optionally substituted by at least one halogenatom;m represents an integer of 0 to 5; provided that, when m represents aninteger of 2 or more, each of R³s is same or different;R⁴ represents a halogen atom, a nitro group, a cyano group, a C1-C4alkyl group optionally substituted by at least one halogen atom or aC1-C4 alkoxy group optionally substituted by at least one halogen atom;R⁵ represents a halogen atom, a nitro group, a cyano group, a C1-C4alkyl group optionally substituted by at least one halogen atom or aC1-C4 alkoxy group optionally substituted by at least one halogen atom;n represents an integer of 0 to 4; provided that, when n represents aninteger of 2 or more, each of R⁵s is same or different.

Next, substituents on the compounds of the present invention and thelike will be described.

As the substituent on the compound of the present invention representedby the formula (1), the compound represented by the formula (2), thecompound represented by the formula (1-3) and the compound representedby the formula (3) of the present invention, groups shown below areexemplified.

The C1-C4 alkoxy group represented by R¹ includes, for example, amethoxy group and an ethoxy group.

The C1-C4 alkyl group represented by R² includes, for example, a methylgroup and an ethyl group.

The C1-C4 alkyl group optionally substituted by at least one halogenatom represented by R³ or R³⁻¹ includes, for example, a methyl group, anethyl group, an isopropyl group, a tert-butyl group, a trifluoromethylgroup, a difluoromethyl group and a fluoromethyl group;

the C1-C4 alkoxy group optionally substituted by at least one halogenatom includes, for example, a methoxy group, an ethoxy group, anisopropoxy group, a trifluoromethoxy group, a difluoromethoxy group, afluoromethoxy group, a chlorodifluoromethoxy group, abromodifluoromethoxy group, a 1,1,2,2-tetrafluoroethoxy group and a2,2,2-trifluoroethoxy group;

the C1-C4 alkylthio group optionally substituted by at least one halogenatom includes, for example, a methylthio group, an ethylthio group, atrifluoromethylthio group and a 1,1,2,2-tetrafluoroethylthio group, and

the halogen atom represented by R³, R³⁻¹, R⁴, and R⁵ includes a fluorineatom, a chlorine atom, a bromine atom and an iodine atom.

The C1-C4 alkyl group optionally substituted by at least one halogenatom represented by R⁴ and R⁵ includes, for example, a methyl group, anethyl group, a trifluoromethyl group, a difluoromethyl group and afluoromethyl group, and

the C1-C4 alkoxy group optionally substituted by at least one halogenatom includes, for example, a methoxy group, an ethoxy group, atrifluoromethoxy group, a difluoromethoxy group and a fluoromethoxygroup.

The phenyl group substituted by R⁴ and (R⁵)_(n) includes, for example,groups in which n is 0, that is, a 2-chlorophenyl group, a2-fluorophenyl group, a 2-nitrophenyl group, a 2-cyanophenyl group, a2-methylphenyl group, a 2-(trifluoromethyl)phenyl group, a2-methoxyphenyl group, a 2-(difluoromethoxy)phenyl group, a2-(trifluoromethoxy)phenyl group; groups in which n is 1, that is, a2,3-difluorophenyl group, a 2,3-dichlorophenyl group, a2,4-difluorophenyl group, a 2-chloro-4-fluorophenyl group, a4-chloro-2-fluorophenyl group, a 2,4-dichlorophenyl group, a2,5-difluorophenyl group, a 2,6-difluorophenyl group, a2-chloro-6-fluorophenyl group, a 2,6-dichlorophenyl group, a2-fluoro-6-methylphenyl group, a 2-fluoro-6-nitrophenyl group, a2-cyano-6-fluorophenyl group, a 2-fluoro-6-(trifluoromethyl)phenylgroup, a 2-(difluoromethoxy)-6-fluorophenyl group, a2-fluoro-6-(trifluoromethoxy)phenyl group, a 2-fluoro-6-methoxyphenylgroup; groups in which n is 2, that is, a 2,3,4-trifluorophenyl group, a2,3,5-trifluorophenyl group, 2,4,5-trifluorophenyl group, a2,3,6-trifluorophenyl group, a 2,4,6-trifluorophenyl group, a2-chloro-4,6-difluorophenyl group, a 4-chloro-2,6-difluorophenyl group,a 2,6-difluoro-4-ethoxyphenyl group, a 2,6-difluoro-4-methoxyphenylgroup, a 2,4-dichloro-6-fluorophenyl group, a2,6-dichloro-4-fluorophenyl group, a 2,4,6-trichlorophenyl group, a2,6-difluoro-4-cyanophenyl group, a 2,6-difluoro-4-nitrophenyl group, a2,6-difluoro-4-(trifluoromethyl)phenyl group, a2,3-difluoro-6-(trifluoromethyl)phenyl group, a2,6-difluoro-3-chlorophenyl group; groups in which n is 3, that is, a2,3,4,5-tetrafluorophenyl group, a 2,3,4,6-tetrafluorophenyl group, a2,3,5,6-tetrafluorophenyl group; groups in which n is 4, that is, a2,3,4,5,6-pentafluorophenyl group, a 4-methoxy-2,3,5,6-tetrafluorophenylgroup, a 4-ethoxy-2,3,5,6-tetrafluorophenyl group, a4-cyano-2,3,5,6-tetrafluorophenyl group, a4-nitro-2,3,5,6-tetrafluorophenyl group and a4-chloro-2,3,5,6-tetrafluorophenyl group.

The phenyl group substituted by (R³)_(m) includes, for example, a phenylgroup; groups in which m is 1, that is, a 4-methylphenyl group, a3-methylphenyl group, a 2-methylphenyl group, a 4-ethylphenyl group, a4-isopropylphenyl group, a 4-tert-butylphenyl group, a4-(trifluoromethyl)phenyl group, a 3-(trifluoromethyl)phenyl group, a4-chlorophenyl group, a 3-chlorophenyl group, a 2-chlorophenyl group, a4-fluorophenyl group, a 3-fluorophenyl group, a 2-fluorophenyl group, a4-methoxyphenyl group, a 3-methoxyphenyl group, a 4-ethoxyphenyl group,a 4-(trifluoromethoxy)phenyl group, a 4-nitrophenyl group, a4-cyanophenyl group, a 4-(methylthio)phenyl group, a4-(trifluoromethylthio)phenyl group; groups in which m is 2, that is, a2,4-dimethylphenyl group, a 2,5-dimethylphenyl group, a3,4-dimethylphenyl group, a 2,4-dichlorophenyl group, a2,5-dichlorophenyl group, a 3,4-dichlorophenyl group, a2,3-difluorophenyl group, a 2,4-difluorophenyl group, a2,5-difluorophenyl group, a 3,4-difluorophenyl group, a3,5-difluorophenyl group, a 4-chloro-2-fluorophenyl group, a2,4-dimethoxyphenyl group and a 3,4-dimethoxyphenyl group.

Embodiments of the compound of the present invention include, forexample, the following compounds in the compounds of the presentinvention.

Pyridazine compounds of the formula (1) in which R¹ is a chlorine atomor a bromine atom;

pyridazine compounds of the formula (1) in which R¹ is a C1-C4 alkoxygroup;

pyridazine compounds of the formula (1) in which R¹ is a chlorine atomand R² is a methyl group;

pyridazine compounds of the formula (1) in which R¹ is a methoxy groupand R² is a methyl group;

pyridazine compounds of the formula (1) in which R³ is a C1-C4 alkylgroup optionally substituted by at least one halogen atom, a C1-C4alkoxy group optionally substituted by at least one halogen atom, or ahalogen atom;

pyridazine compounds of the formula (1) in which R³ is a C1-C4 alkylgroup or a halogen atom;

pyridazine compounds of the formula (1) in which R³ is a methyl group, atrifluoromethyl group, a chlorine atom, a fluorine atom or a methoxygroup;

pyridazine compounds of the formula (1) in which R³ is a methyl group, achlorine atom or a fluorine atom;

pyridazine compounds of the formula (1) in which m is 1 or 2;

pyridazine compounds of the formula (1) in which m is 1;

pyridazine compounds of the formula (1) in which m is 2;

pyridazine compounds of the formula (1) in which m is 1 and R³ is asubstituent at 4-position of benzene ring;

pyridazine compounds of the formula (1) in which m is 1, R³ is a halogenatom, a C1-C4 alkyl group optionally substituted by at least one halogenatom or a C1-C4 alkoxy group optionally substituted by at least onehalogen atom, and R³ is a substituent at 4-position of benzene ring;

pyridazine compounds of the formula (1) in which m is 1, R³ is a halogenatom or a C1-C4 alkyl group optionally substituted by at least onehalogen atom, and R³ is a substituent at 4-position of benzene ring;

pyridazine compounds of the formula (1) in which m is 1, R³ is a halogenatom or a C1-C4 alkyl group, and R³ is a substituent at 4-position ofbenzene ring;

pyridazine compounds of the formula (1) in which m is 1, R³ is a methylgroup, a trifluoromethyl group, a chlorine atom, a fluorine atom or amethoxy group, and R³ is a substituent at 4-position of benzene ring;

pyridazine compounds of the formula (1) in which m is 1, R³ is a methylgroup, a chlorine atom or a fluorine atom, and R³ is a substituent at4-position of benzene ring;

pyridazine compounds of the formula (1) in which R⁴ is a halogen atom;

pyridazine compounds of the formula (1) in which R⁴ is a fluorine atom;

pyridazine compounds of the formula (1) in which R⁴ is a chlorine atom;

pyridazine compounds of the formula (1) in which R⁴ is a fluorine atomor a chlorine atom;

pyridazine compounds of the formula (1) in which n is 0, 1 or 2;

pyridazine compounds of the formula (1) in which n is 0;

pyridazine compounds of the formula (1) in which n is 1;

pyridazine compounds of the formula (1) in which n is 2;

pyridazine compounds of the formula (1) in which n is 1 or 2 and R⁵ is ahalogen atom,

pyridazine compounds of the formula (1) in which n is 1, R⁵ is a halogenatom, and R⁵ is a substituent at 4-position or 6-position of benzenering;

pyridazine compounds of the formula (1) in which n is 2, R⁵ is a halogenatom, and R⁵ is a substituent at 4-position or 6-position of benzenering;

pyridazine compounds of the formula (1) in which n is 1, R⁵ is afluorine atom, and R⁵ is a substituent at 4-position or 6-position ofbenzene ring;

pyridazine compounds of the formula (1) in which n is 2, R⁵ is afluorine atom, and R⁵ is a substituent at 4-position or 6-position ofbenzene ring;

pyridazine compounds of the formula (1) in which R⁴ is a halogen atom, nis 1 or 2, and R⁵ is a halogen atom;

pyridazine compounds of the formula (1) in which n is 1, R⁴ is a halogenatom, R⁵ is a halogen atom, and R⁵ is a substituent at 4-position or6-position of benzene ring;

pyridazine compounds of the formula (1) in which n is 2, R⁴ is a halogenatom, R⁵ is a halogen atom, and R⁵ is a substituent at 4-position or6-position of benzene ring;

pyridazine compounds of the formula (1) in which n is 1, R⁴ is afluorine atom, R⁵ is a fluorine atom, and R⁵ is a substituent at4-position or 6-position of benzene ring;

pyridazine compounds of the formula (1) in which n is 2, R⁴ is afluorine atom, R⁵ is a fluorine atom, and R⁵ is a substituent at4-position or 6-position of benzene ring;

pyridazine compounds of the formula (1) in which m is 1 or 2, and n is0, 1 or 2;

pyridazine compounds of the formula (1) in which R¹ is a chlorine atomor a bromine atom, R² is a methyl group, and R⁴ is a halogen atom; and

pyridazine compounds of the formula (1) in which m is 1 or 2, n is 0, 1or 2, R¹ is a chlorine atom or a bromine atom, R² is a methyl group, andR⁴ is a halogen atom.

Embodiments of the compound represented by the formula (2), the compoundrepresented by the formula (1-3) and the compound represented by theformula (3), which are intermediates of the compound of the presentinvention, include, for example, compounds described below.

Embodiments of the compound represented by the formula (2) include, forexample, the following compounds.

Compounds of the formula (2) in which m is 1 or 2, and n is 0, 1 or 2;

compounds of the formula (2) in which R² is a methyl group, and R⁴ is ahalogen atom; and

compounds of the formula (2) in which m is 1 or 2, n is 0, 1 or 2, R² isa methyl group, and R⁴ is a halogen atom.

Embodiments of the compound represented by the formula (1-3) include,for example, the following compounds.

Compounds of the formula (1-3) in which m is 1 or 2;

compounds of the formula (1-3) in which R¹ is a chlorine atom or abromine atom, R² is a methyl group, and R⁴ is a halogen atom; and

compounds of the formula (1-3) in which m is 1 or 2, R¹ is a chlorineatom or a bromine atom, R² is a methyl group, and R⁴ is a halogen atom.

Embodiments of the compound represented by the formula (3) include, forexample, the following compounds.

Compounds of the formula (3) in which m is 1 or 2, and n is 0, 1 or 2;

compounds of the formula (3) in which R² is a methyl group, and R⁴ is ahalogen atom; and

compounds of the formula (3) in which m is 1 or 2, n is 0, 1 or 2, R² isa methyl group, and R⁴ is a halogen atom.

Next, the method of producing the compound of the present invention willbe described,

The compound of the present invention can be produced, for example, bythe following (Production method 1), (Production method 2) and(Production method 3).

(Production Method 1)

The compound represented by the formula (1-1) in which R¹ is a chlorineatom or a bromine atom, among the compounds of the present invention,can be produced by reacting the compound represented by the formula (2)with a halogenating agent.

(wherein,

R² is a C1-C4 alkyl group,

R³ is a halogen atom, a nitro group, a cyano group, a C1-C4 alkyl groupoptionally substituted by at least one halogen atom, a C1-C4 alkoxygroup optionally substituted by at least one halogen atom, or a C1-C4alkylthio group optionally substituted by at least one halogen atom,

m is an integer of 0 to 5; provided that, when m is an integer of 2 ormore, each of R³s is same or different;

R⁴ is a halogen atom, a nitro group, a cyano group, a C1-C4 alkyl groupoptionally substituted by at least one halogen atom or a C1-C4 alkoxygroup optionally substituted by at least one halogen atom,

R⁵ is a halogen atom, a nitro group, a cyano group, a C1-C4 alkyl groupoptionally substituted by at least one halogen atom or a C1-C4 alkoxygroup optionally substituted by at least one halogen atom,

n is an integer of 0 to 4; provided that, when n is an integer of 2 ormore, each of R⁵s is same or different.

R¹¹ is a chlorine atom or a bromine atom.).

The reaction is carried out in the absence or presence of a solvent.

Examples of the solvent used in the reaction include hydrocarbons suchas toluene, xylene and the like, halogenated hydrocarbons such aschlorobenzene, dichlorobenzene and the like, and mixtures thereof.

The halogenating agent used in the reaction includes, for example,chlorinating agents such as phosphorus oxychloride, phosphoruspentachloride, and brominating agents such as phosphorus oxybromide,phosphorus pentabromide, and the like.

The amount of the halogenating agent used in the reaction is usually aproportion of 1 to 20 mol per 1 mol of the compound represented by theformula (2).

The reaction temperature is usually in a range of 20 to 120° C., and thereaction time is usually in a range of 0.1 to 8 hours.

After completion of the reaction, for example, the reaction mixture issubjected to a post treatment operation such as the reaction mixturebeing concentrated, water being added to the residue and extracting withan organic solvent, and the resulting organic layer being dried,concentration and the like; thus, the compound represented by theformula (1-1) can be isolated. The compound represented by the formula(1-1) isolated can also be further purified by chromatography,re-crystallization and the like.

(Production Method 2)

The compound represented by the formula (1-2) in which R¹ is a C1-C4alkoxy group, among the compounds of the present invention, can beproduced by reacting the compound represented by the formula (1-1) withan alcoholate compound represented by the formula:NaR¹²(wherein, R¹² is a C1-C4 alkoxy group).

(wherein, R¹¹, R², R³, m, R⁴, R⁵, n and R¹² are the same meanings asdescribed above).

The reaction is carried out usually in a solvent.

Examples of the solvent used in the reaction include alcoholsrepresented by the formula R¹²H, ethers such as tetrahydrofuran,1,2-dimethoxyethane and the like, and mixtures thereof.

The amount of the alcoholate compound used in the reaction is usually aproportion of 1 to 20 mol per 1 mol of the compound represented by theformula (1-1).

The reaction temperature is usually in a range of 0 to 120° C., and thereaction time is usually in a range of 1 to 72 hours.

After completion of the reaction, for example, the reaction mixture issubjected to a post treatment operation such as water being added to thereaction mixture and extracting with an organic solvent, and theresulting organic layer being dried, concentration and the like; thus,the compound represented by the formula (1-2) can be isolated. Thecompound-represented by the formula (1-2) isolated can also be furtherpurified by chromatography, re-crystallization and the like.

(Production Method 3)

The compound represented by the formula (1-4), among the compounds ofthe present invention, can be produced by reacting the compoundrepresented by the formula (1-3) with alkyl nitrite and copper halide(II).

(wherein, R² and m are the same meanings as described above, R¹ is achlorine atom, a bromine atom or a C1-C4 alkoxy group, R³⁻¹ is a halogenatom, a cyano group, a C1-C4 alkyl group optionally substituted by atleast one halogen atom, a C1-C4 alkoxy group optionally substituted byat least one halogen atom, or a C1-C4 alkylthio group optionallysubstituted by at least one halogen atom, and R¹³ is a chlorine atom ora bromine atom.).

The reaction is carried out usually in a solvent.

Examples of the solvent used in the reaction include acetonitrile,propionitrile and the like. The alkyl nitrite used in the reactionincludes, for example, tert-butyl nitrite and isoamylnitrite, and thecopper halide (II) includes, for example, copper chloride (II) andcopper bromide (II), and these are selected depending on the kind of R¹³of the compound represented by the formula (1-4).

The amounts of the alkyl nitrite and the copper halide (II) used in thereaction are each usually a proportion of 1 to 2 mol per 1 mol of thecompound represented by the formula (1-3).

The reaction temperature is usually in a range of 0 to 50° C., and thereaction time is usually in a range of 1 to 24 hours.

After completion of the reaction, for example, the reaction mixture issubjected to a post treatment operation such as water being added to thereaction mixture and extracting with an organic solvent, and theresulting organic layer being dried, concentration and the like; thus,the compound represented by the formula (1-4) can be isolated. Thecompound represented by the formula (1-4) isolated can also be furtherpurified by chromatography, re-crystallization and the like.

Next, examples of production of intermediates of the compound of thepresent invention will be shown as Reference Production Methods.

(Reference Production Method 1)

(wherein, R², R³, m, R⁴, R⁵ and n are the same meanings as describedabove).

The compound represented by the formula (2) an be produced by reactingthe compound represented by the formula (3) with hydrazine.

The reaction is carried out usually in a solvent.

The solvent used in the reaction includes, for example, alcohols such asmethanol, ethanol, propanol, isopropanol, butanol and the like, etherssuch as tetrahydrofuran, 1,2-dimethoxyethane and the like, and mixturesthereof.

The amount of hydrazine used in the reaction is usually a proportion of1 to 5 mol per 1 mol of the compound represented by the formula (3).Hydrazine used in the reaction may be its hydrate.

The reaction temperature is usually in a range of 0 to 120° C., and thereaction time is usually in a range of 1 to 24 hours.

After completion of the reaction, the compound represented by theformula (2) can be isolated by subjecting to a post treatment operationsuch as cooling the reaction mixture to deposit solid which is thenfiltrated, or subjecting the reaction mixture to concentrate and thelike. The compound represented by the formula (2) isolated can also befurther purified by chromatography, re-crystallization and the like.

(Reference Production Method 2)

The compound represented by the formula (3) can be produced according tothe following scheme.

(wherein, R², R³, m, R⁴, R⁵ and n are the same meanings as describedabove).

The production method shown in the above-mentioned scheme is composed ofa process (ii-a), process (ii-b) and process (ii-c)

The reaction in the process (ii-a) can be carried out, for example, bymixing the compound represented by the formula (4); the compoundrepresented by the formula (5); an acyclic tertiary amine such astriethylamine, diisopropylethylamine and the like; and a solvent.

The solvent used in the reaction includes, for example, nitriles such asacetonitrile, propionitrile and the like.

Regarding the amount of the reagent used in the reaction, the proportionof the compound represented by the formula (5) is usually 0.8 to 1.3 moland the proportion of a weak base is usually 0.8 to 1.3 mol, per 1 molof the compound represented by the formula (4).

The reaction temperature is usually in a range of 0 to 50° C., and thereaction time is usually in a range of 1 to 48 hours.

After completion of the reaction, the reaction mixture can be useditself in the reaction of the process (ii-b).

The reaction of the process (ii-b) can be carried out, for example, bymixing the reaction mixture obtained by the reaction of the process(ii-a) with at least one cyclic amine compound selected from1,8-diazabicyclo[5.4.0]undec-7-ene (DBU),1,5-diazabicyclo[4.3.0]non-5-ene (DBN) and1,4-diazabicyclo[2.2.2]octane(triethylenediamine).

The amount of the cyclic amine compound used in the reaction is usuallya proportion of 1 to 3 mol per 1 mol of the compound represented by theformula (6).

The reaction temperature is usually in a range of −20 to 50° C., and thereaction time is usually in a range of 1 to 8 hours.

After completion of the reaction, the reaction mixture can be used as itis in the reaction of the process (ii-c).

The reaction of the process (ii-c) can be carried out, for example, byblowing a gas containing oxygen into the reaction mixture obtained bythe reaction of the process (ii-b).

The gas containing oxygen used in this reaction includes, for example,oxygen and air.

The reaction temperature is usually in a range of 0 to 50° C., and thereaction time is usually in a range of 1 to 24 hours.

After completion of the reaction of the process (ii-c), the reactionmixture is subjected to a post treatment operation such as dilutehydrochloric acid being added to the reaction mixture and extractingwith an organic solvent, and the resulting organic layer being dried,concentration and the like; thus, the compound represented by theformula (3) can be isolated. The compound represented by the formula (3)isolated can also be further purified by chromatography,re-crystallization and the like.

(Reference Production Method 3)

(wherein, R², R³ and m are the same meanings as described above)

The compound represented by the formula (4) can be produced by reactingthe compound represented by the formula (8) with bromine.

The reaction is carried out usually in a solvent.

The solvent used in the reaction includes, for example, acetic acid.

The amount of bromine used in the reaction is usually a proportion of0.8 to 1.3 mol per 1 mol of the compound represented by the formula (8).

The reaction temperature is usually in a range of −10 to 40° C., and thereaction time is usually in a range of 0.1 to 24 hours.

The reaction can also be carried out in the presence of catalytic amountof hydrobromic acid.

After completion of the reaction, the reaction mixture is subjected to apost treatment operation such as the reaction mixture beingconcentrated, or water being added to the reaction mixture andextracting with an organic solvent, the organic layer being washed by asodium hydrogen carbonate aqueous solution and water, and being dried,concentration and the like is carried out; thus, the compoundrepresented by the formula (4) can be isolated. The compound representedby the formula (4) isolated can also be further purified bychromatography, re-crystallization and the like.

(Reference Production Method 4)

The compound represented by the formula (1-3) can be produced bysubjecting the compound represented by the formula (1-5) to a reductionreaction.

(wherein, R¹, R², R³⁻¹ and m are the same meanings as described above).

The reaction is carried out, for example, in a mixed solvent of water,acetic acid and ethyl acetate in the presence of iron.

The amount of iron used in the reaction is usually a proportion of 4 to10 mol per 1 mol of the compound represented by the formula (1-5).

The reaction temperature is usually in a range of 20 to 100° C., and thereaction time is usually in a range of 0.1 to 24 hours.

After completion of the reaction, the reaction mixture is subjected to apost treatment operation such as water being added to the reactionmixture and extracting with an organic solvent, and the organic layerbeing dried, concentration and the like, thus, the compound representedby the formula (1-3) can be isolated. The compound represented by theformula (1-3) isolated can also be further purified by chromatography,re-crystallization and the like.

Next, specific examples of the compound of the present invention will beshown.

Pyridazine compound represented by the formula (1-a)

Pyridazine compound represented by the formula (1-b)

In the formula (1-a) or (1-b), (R³)_(m) and Y represent one combinationof substituents shown in Table 1.

TABLE 1 (R³)_(m) Y 4-CH₃ 2,4,6-trifluorophenyl 3-CH₃2,4,6-trifluorophenyl 2-CH₃ 2,4,6-trifluorophenyl 4-CF₃2,4,6-trifluorophenyl 4-Cl 2,4,6-trifluorophenyl 3-Cl2,4,6-trifluorophenyl 2-Cl 2,4,6-trifluorophenyl 4-F2,4,6-trifluorophenyl 4-NO₂ 2,4,6-trifluorophenyl 4-CN2,4,6-trifluorophenyl 4-OCH₃ 2,4,6-trifluorophenyl 4-OCF₃2,4,6-trifluorophenyl 4-OCHF₂ 2,4,6-trifluorophenyl 4-OCClF₂2,4,6-trifluorophenyl 4-OCBrF₂ 2,4,6-trifluorophenyl 4-SCH₃2,4,6-trifluorophenyl 4-SCF₃ 2,4,6-trifluorophenyl —2,4,6-trifluorophenyl 4-CH₃ 2-chlorophenyl 4-Cl 2-chlorophenyl 4-CH₃2-fluorophenyl 4-Cl 2-fluorophenyl 2-Cl, 4-Cl 2,4,6-trifluorophenyl3-Cl, 4-Cl 2,4,6-trifluorophenyl 2-CH₃,4-CH₃ 2,4,6-trifluorophenyl3-CH₃,4-CH₃ 2,4,6-trifluorophenyl 3-OCH₃,4-OCH₃ 2,4,6-trifluorophenyl2-F, 4-F 2,4,6-trifluorophenyl 2-F, 4-Cl 2,4,6-trifluorophenyl 4-CH₃2-nitrophenyl 4-Cl 2-nitrophenyl 4-CH₃ 2-cyanophenyl 4-Cl 2-cyanophenyl4-CH₃ 2-chloro-6-fluorophenyl 4-CF₃ 2-chloro-6-fluorophenyl 4-Cl2-chloro-6-fluorophenyl 4-F 2-chloro-6-fluorophenyl 4-OCH₃2-chloro-6-fluorophenyl 2-Cl, 4-Cl 2-chloro-6-fluorophenyl 3-Cl, 4-Cl2-chloro-6-fluorophenyl 2-CH₃,4-CH₃ 2-chloro-6-fluorophenyl 3-CH₃,4-CH₃2-chloro-6-fluorophenyl 2-F, 4-F 2-chloro-6-fluorophenyl 2-F, 4-Cl2-chloro-6-fluorophenyl 4-CH₃ 2,6-difluoro-4-methoxyphenyl 4-CF₃2,6-difluoro-4-methoxyphenyl 4-Cl 2,6-difluoro-4-methoxyphenyl 4-F2,6-difluoro-4-methoxyphenyl 4-OCH₃ 2,6-difluoro-4-methoxyphenyl 2-Cl,4-Cl 2,6-difluoro-4-methoxyphenyl 3-Cl, 4-Cl2,6-difluoro-4-methoxyphenyl 2-CH₃,4-CH₃ 2,6-difluoro-4-methoxyphenyl3-CH₃,4-CH₃ 2,6-difluoro-4-methoxyphenyl 2-F, 4-F2,6-difluoro-4-methoxyphenyl 2-F, 4-Cl 2,6-difluoro-4-methoxyphenyl4-CH₃ 2,6-difluoro-4-ethoxyphenyl 4-Cl 2,6-difluoro-4-ethoxyphenyl 4-CH₃2-methylphenyl 4-Cl 2-methylphenyl 4-CH₃ 2-(trifluoromethyl)phenyl 4-Cl2-(trifluoromethyl)phenyl 4-CH₃ 2,6-difluorophenyl 3-CH₃2,6-difluorophenyl 2-CH₃ 2,6-difluorophenyl 4-CF₃ 2,6-difluorophenyl4-Cl 2,6-difluorophenyl 3-Cl 2,6-difluorophenyl 2-Cl 2,6-difluorophenyl4-F 2,6-difluorophenyl 4-NO₂ 2,6-difluorophenyl 4-CN 2,6-difluorophenyl4-OCH₃ 2,6-difluorophenyl 4-OCF₃ 2,6-difluorophenyl 4-OCHF₂2,6-difluorophenyl 4-OCClF₂ 2,6-difluorophenyl 4-OCBrF₂2,6-difluorophenyl 4-SCH₃ 2,6-difluorophenyl 4-SCF₃ 2,6-difluorophenyl —2,6-difluorophenyl 2-Cl, 4-Cl 2,6-difluorophenyl 3-Cl, 4-Cl2,6-difluorophenyl 2-Cl, 4-CH₃ 2,6-difluorophenyl 3-CH₃,4-CH₃2,6-difluorophenyl 3-OCH₃,4-OCH₃ 2,6-difluorophenyl 2-F, 4-F2,6-difluorophenyl 2-F, 4-Cl 2,6-difluorophenyl 4-CH₃ 2,4-difluorophenyl4-CF₃ 2,4-difluorophenyl 4-Cl 2,4-difluorophenyl 4-F 2,4-difluorophenyl4-OCH₃ 2,4-difluorophenyl 2-Cl, 4-Cl 2,4-difluorophenyl 3-Cl, 4-Cl2,4-difluorophenyl 2-CH₃, 4-CH₃ 2,4-difluorophenyl 3-CH₃, 4-CH₃2,4-difluorophenyl 2-F, 4-F 2,4-difluorophenyl 2-F, 4-Cl2,4-difluorophenyl 4-CH₃ 2,3,4-trifluorophenyl 4-Cl2,3,4-trifluorophenyl 4-CH₃ 2,3,5-trifluorophenyl 4-Cl2,3,5-trifluorophenyl 4-CH₃ 2,3,6-trifluorophenyl 4-Cl2,3,6-trifluorophenyl 4-CH₃ 2,4,5-trifluorophenyl 4-Cl2,3,5-trifluorophenyl 4-CH₃ 2,3-difluorophenyl 4-Cl 2,3-difluorophenyl4-CH₃ 2,5-difluorophenyl 4-Cl 2,5-difluorophenyl 4-CH₃2-(difluoromethoxy)phenyl 4-Cl 2-(difluoromethoxy)phenyl 4-CH₃2-(trifluoromethoxy)phenyl 4-Cl 2-(trifluoromethoxy)phenyl 4-CH₃2-methoxyphenyl 4-Cl 2-methoxyphenyl 4-Cl pentafluorophenyl 4-Cl4-methoxy-2,3,5,6-tetrafluorophenyl 4-Cl4-ethoxy-2,3,5,6-tetrafluorophenyl 4-Cl4-cyano-2,3,5,6-tetrafluorophenyl 4-Cl 4-nitro-2,3,5,6-tetrafluorophenyl4-Cl 2,3,5,6-tetrafluorophenyl 4-Cl 2,6-difluoro-4-cyanophenyl 4-Cl2,6-difluoro-4-nitrophenyl 4-Cl 2,6-difluoro-4-chlorophenyl 4-Cl2,6-difluoro-4-(trifluoromethyl)phenyl 4-Cl 2-fluoro-6-methylphenyl 4-Cl2-fluoro-6-nitrophenyl 4-Cl 2-cyano-6-fluorophenyl 4-Cl2-fluoro-6-(trifluoromethyl)phenyl 4-Cl2-(difluoromethoxy)-6-fluorophenyl 4-Cl2-fluoro-6-(trifluoromethoxy)-phenyl 4-Cl 2-fluoro-6-methoxyphenyl 4-Cl2,3-difluoro-6-(trifluoromethyl)phenyl 4-Cl 2,6-difluoro-3-chlorophenylIn the table, “—” means that m is 0.

Next, specific examples of the intermediate of the compound of thepresent invention will be shown below.

The compound represented by the formula (2-a):

The compound represented by the formula (3-a):

The compound represented by the formula (6-a):

The compound represented by the formula (7-a):

In the formula (2-a), (3-a), (6-a) or (7-a), (R³)_(m) and Y representone combination of substituents shown in Table 2.

TABLE 2 (R³)_(m) Y 4-CH₃ 2,4,6-trifluorophenyl 3-CH₃2,4,6-trifluorophenyl 2-CH₃ 2,4,6-trifluorophenyl 4-CF₃2,4,6-trifluorophenyl 4-Cl 2,4,6-trifluorophenyl 3-Cl2,4,6-trifluorophenyl 2-Cl 2,4,6-trifluorophenyl 4-F2,4,6-trifluorophenyl 4-NO₂ 2,4,6-trifluorophenyl 4-CN2,4,6-trifluorophenyl 4-OCH₃ 2,4,6-trifluorophenyl 4-OCF₃2,4,6-trifluorophenyl 4-OCHF₂ 2,4,6-trifluorophenyl 4-OCClF₂2,4,6-trifluorophenyl 4-OCBrF₂ 2,4,6-trifluorophenyl 4-SCH₃2,4,6-trifluorophenyl 4-SCF₃ 2,4,6-trifluorophenyl —2,4,6-trifluorophenyl 4-CH₃ 2-chlorophenyl 4-Cl 2-chlorophenyl 4-CH₃2-fluorophenyl 4-Cl 2-fluorophenyl 2-Cl, 4-Cl 2,4,6-trifluorophenyl3-Cl, 4-Cl 2,4,6-trifluorophenyl 2-CH₃,4-CH₃ 2,4,6-trifluorophenyl3-CH₃,4-CH₃ 2,4,6-trifluorophenyl 3-OCH₃,4-OCH₃ 2,4,6-trifluorophenyl2-F, 4-F 2,4,6-trifluorophenyl 2-F, 4-Cl 2,4,6-trifluorophenyl 4-CH₃2-chloro-6-fluorophenyl 4-CF₃ 2-chloro-6-fluorophenyl 4-Cl2-chloro-6-fluorophenyl 4-F 2-chloro-6-fluorophenyl 4-OCH₃2-chloro-6-fluorophenyl 2-Cl, 4-Cl 2-chloro-6-fluorophenyl 3-Cl, 4-Cl2-chloro-6-fluorophenyl 2-CH₃,4-CH₃ 2-chloro-6-fluorophenyl 3-CH₃,4-CH₃2-chloro-6-fluorophenyl 2-F, 4-F 2-chloro-6-fluorophenyl 2-F, 4-Cl2-chloro-6-fluorophenyl 4-CH₃ 2-methylphenyl 4-Cl 2-methylphenyl 4-CH₃2-(trifluoromethyl)phenyl 4-Cl 2-(trifluoromethyl)phenyl 4-CH₃2,6-difluoro-4-methoxyphenyl 4-CF₃ 2,6-difluoro-4-methoxyphenyl 4-Cl2,6-difluoro-4-methoxyphenyl 4-F 2,6-difluoro-4-methoxyphenyl 4-OCH₃2,6-difluoro-4-methoxyphenyl 2-Cl, 4-Cl 2,6-difluoro-4-methoxyphenyl3-Cl, 4-Cl 2,6-difluoro-4-methoxyphenyl 2-CH₃, 4-CH₃2,6-difluoro-4-methoxyphenyl 3-CH₃, 4-CH₃ 2,6-difluoro-4-methoxyphenyl2-F, 4-F 2,6-difluoro-4-methoxyphenyl 2-F, 4-Cl2,6-difluoro-4-methoxyphenyl 4-CH₃ 2,6-difluoro-4-ethoxyphenyl 4-Cl2,6-difluoro-4-ethoxyphenyl 4-CH₃ 2-nitrophenyl 4-Cl 2-nitrophenyl 4-CH₃2-cyanophenyl 4-Cl 2-cyanophenyl 4-CH₃ 2,6-difluorophenyl 3-CH₃2,6-difluorophenyl 2-CH₃ 2,6-difluorophenyl 4-CF₃ 2,6-difluorophenyl4-Cl 2,6-difluorophenyl 3-Cl 2,6-difluorophenyl 2-Cl 2,6-difluorophenyl4-F 2,6-difluorophenyl 4-NO₂ 2,6-difluorophenyl 4-CN 2,6-difluorophenyl4-OCH₃ 2,6-difluorophenyl 4-OCF₃ 2,6-difluorophenyl 4-OCHF₂2,6-difluorophenyl 4-OCClF₂ 2,6-difluorophenyl 4-OCBrF₂2,6-difluorophenyl 4-SCH₃ 2,6-difluorophenyl 4-SCF₃ 2,6-difluorophenyl —2,6-difluorophenyl 2-Cl, 4-Cl 2,6-difluorophenyl 3-Cl, 4-Cl2,6-difluorophenyl 2-Cl, 4-CH₃ 2,6-difluorophenyl 3-CH₃, 4-CH₃2,6-difluorophenyl 3-OCH₃, 4-OCH₃ 2,6-difluorophenyl 2-F, 4-F2,6-difluorophenyl 2-F, 4-Cl 2,6-difluorophenyl 4-CH₃ 2,4-difluorophenyl4-CF₃ 2,4-difluorophenyl 4-Cl 2,4-difluorophenyl 4-F 2,4-difluorophenyl4-OCH₃ 2,4-difluorophenyl 2-Cl, 4-Cl 2,4-difluorophenyl 3-Cl, 4-Cl2,4-difluorophenyl 2-CH₃, 4-CH₃ 2,4-difluorophenyl 3-CH₃, 4-CH₃2,4-difluorophenyl 2-F, 4-F 2,4-difluorophenyl 2-F, 4-Cl2,4-difluorophenyl 4-CH₃ 2,3,4-trifluorophenyl 4-Cl2,3,4-trifluorophenyl 4-CH₃ 2,3,5-trifluorophenyl 4-Cl2,3,5-trifluorophenyl 4-CH₃ 2,3,6-trifluorophenyl 4-Cl2,3,6-trifluorophenyl 4-CH₃ 2,3,5-trifluorophenyl 4-Cl2,3,5-trifluorophenyl 4-CH₃ 2,3-difluorophenyl 4-Cl 2,3-difluorophenyl4-CH₃ 2,5-difluorophenyl 4-Cl 2,5-difluorophenyl 4-CH₃2-(difluoromethoxy)phenyl 4-Cl 2-(difluoromethoxy)phenyl 4-CH₃2-(trifluoromethoxy)phenyl 4-Cl 2-(trifluoromethoxy)phenyl 4-CH₃2-methoxyphenyl 4-Cl 2-methoxyphenyl 4-Cl pentafluorophenyl 4-Cl4-methoxy-2,3,5,6-tetrafluorophenyl 4-Cl4-ethoxy-2,3,5,6-tetrafluorophenyl 4-Cl4-cyano-2,3,5,6-tetrafluorophenyl 4-Cl 4-nitro-2,3,5,6-tetrafluorophenyl4-Cl 2,3,5,6-tetrafluorophenyl 4-Cl 2,6-difluoro-4-cyanophenyl 4-Cl2,6-difluoro-4-nitrophenyl 4-Cl 2,6-difluoro-4-chlorophenyl 4-Cl2,6-difluoro-4-(trifluoromethyl)phenyl 4-Cl 2-fluoro-6-methylphenyl 4-Cl2-fluoro-6-nitrophenyl 4-Cl 2-cyano-6-fluorophenyl 4-Cl2-fluoro-6-(trifluoromethyl)phenyl 4-Cl2-(difluoromethoxy)-6-fluorophenyl 4-Cl2-fluoro-6-(trifluoromethoxy)phenyl 4-Cl 2-fluoro-6-methoxyphenyl 4-Cl2,3-difluoro-6-(trifluoromethyl)phenyl 4-Cl 2,6-difluoro-3-chlorophenylIn the table, “—” means that m is 0.The compound represented by the formula (4-a):

The compound represented by the formula (8-a):

In the formula (4-a) or (8-a), (R³)_(m) represents one of substituentshown in Table 3.

TABLE 3 (R³)_(m) 4-CH₃ 3-CH₃ 2-CH₃ 4-CF₃ 4-Cl 3-Cl 2-Cl 4-F 4-NO₂ 4-CN4-OCH₃ 4-OCF₃ 4-OCHF₂ 4-OCClF₂ 4-OCBrF₂ 4-SCH₃ 4-SCF₃ — 2-Cl, 4-Cl 3-Cl,4-Cl 2-CH₃, 4-CH₃ 3-CH₃, 4-CH₃ 3-OCH₃, 4-OCH₃ 2-F, 4-F 2-F, 4-Cl In thetable, “—” means that m is 0.

The compound represented by the formula (5-a):

In the formula (5-a), Y represents one of substituent shown in Table 4.

TABLE 4 Y 2,4,6-trifluorophenyl 2-chloro-6-fluorophenyl2,6-difluoro-4-methoxyphenyl 2,6-difluoro-4-ethoxyphenyl2,6-difluorophenyl 2,4-difluorophenyl 2,3,4-trifluorophenyl2,3,5-trifluorophenyl 2,3,6-trifluorophenyl 2,4,5-trifluorophenyl2,3-difluorophenyl 2,5-difluorophenyl 2-chlorophenyl 2-fluorophenyl2-nitrophenyl 2-cyanophenyl 2-methylphenyl 2-(trifluoromethyl)phenyl2-(difluoromethoxy)phenyl 2-(trifluoromethoxy)phenyl 2-methoxyphenylpentafluorophenyl 4-methoxy-2,3,5,6-tetrafluorophenyl4-ethoxy-2,3,5,6-tetrafluorophenyl 4-cyano-2,3,5,6-tetrafluorophenyl4-nitro-2,3,5,6-tetrafluorophenyl 2,3,5,6-tetrafluorophenyl2,6-difluoro-4-cyanophenyl 2,6-difluoro-4-nitrophenyl2,6-difluoro-4-chlorophenyl 2,6-difluoro-4-(trifluoromethyl)phenyl2-fluoro-6-methylphenyl 2-fluoro-6-nitrophenyl 2-cyano-6-fluorophenyl2-fluoro-6-(trifluoromethyl)phenyl 2-(difluoromethoxy)-6-fluorophenyl2-fluoro-6-(trifluoromethoxy)phenyl 2-fluoro-6-methoxyphenyl2,3-difluoro-6-(trifluoromethyl)phenyl 2,6-difluoro-3-chlorophenyl

The plant diseases to be controlled by the present compound will beexemplified below.

Pyricularia oryzae, Cochliobolus miyabeanus and Rhizoctonia solani ofrice;

Erysiphe graminis, Gibberella zeae, Puccinia struiformis, P. graminis,P. recondita, P. hordei, Typhula sp., Micronectriella nivalis, Ustilagotritici, U. nuda, Tilletia caries, Pseudocercosporella herpotrichoides,Rhynchosporium secalis, Septoria tritici and Leptosphaeria nodorum, ofwheat and barley;Diaporthe citri, Elsinoe fawcetti, Penicillium digitatum and P. italicumof citrus;Sclerotinia mali, Valsa mali, Podosphaera leucotricha, Alternaria maliand Venturia inaequalis of apple;Venturia nashicola, V. pirina, Alternaria kikuchiana and Gymnosporangiumharaeanum of pear;Sclerotinia cinerea, Cladosporium carpophilum and Phomopsis sp. ofpeach;Elsinoe ampelina, Glomerella cingulata, Uncinula necator, Phakopsoraampelopsidis, Guignardia bidwellil and Plasmopara viticola, of grape;Gloeosporium kaki, Cercospora kaki and Mycosphaerella nawae of Japanesepersimmon;Colletotrichum lagenarium, Sphaerotheca fuliginea, Mycosphaerellamelonis, Fusarium oxysporum, Pseudoperonospora cubensis Phytophthora sp.and Pythium sp. of cucurbit;Alternaria solani, Cladosporium fulvum and Phytophthora infestans oftomato;Phomopsis vexans and Erysiphe cichoracearum, of eggplant;Alternaria japonica and Cercosporella brassicae of Cruciferaevegetables;Puccinia allii of green onion; Cercospora kikuchii, Elsinoe glycines andDiaporthe phaseolorum var. sojae of soybean;Colletotrichum lindemthianum of kidney bean; Cercospora personata andCercospora arachidicola of peanut;Erysiphe pisi of pea;Alternaria solani and Phytophthora infestans of potato;Sphaerotheca humuli of strawberry; Exobasidium reticulatum and Elsinoeleucospila of tea;Alternaria longipes, Erysiphe cichoracearum, Colletotrichum tabacum,Peronospora tabacina and Phytophthora nicotianae of tobacco;Cercospora beticola of sugar beet;Diplocarpon rosae and Sphaerotheca pannosa of rose;Septoria chrysanthemi-indici and Puccinia horiana of chrysanthemum;Botrytis cinerea and Sclerotinia sclerotiorum of various crops;Alternaria brassicicola of radish;and Sclerotinia homeocarpa and Rhizoctonia solani of turf.

Fungicidal effect may be shown by treating the compound of the presentinvention as it is to plants or soils. But, usually, it is used by theform of composition comprising the compound of the present invention anda carrier. Namely, the fungicidal composition of the present inventionis formulated to an emulsifiable concentrate, a wettable powder, a waterdispersible granule, a flowable, a dust, a granule and the like bymixing the compound of the present invention and a solid carrier and/ora liquid carrier and, if necessary, adding other adjuvant forformulation such as surfactant.

These formulations usually contain 0.1 to 90% by weight of the compoundof the present invention.

Solid carriers used for formulation include, for example, fine powdersor granules of minerals such as kaolin clay, attapulgite clay,bentonite, montmorillonite, terra alba, pyrophyllite, talc, diatomaceousearth, calcite and the like; natural organic substances such as corncobpowder, walnut shell powder and the like; synthetic organic substancessuch as urea and the like; salts such as calcium carbonate, ammoniumsulfate and the like; synthetic inorganic substances such as synthetichydrous silicon oxide and the like. Liquid carriers include, forexample, aromatic hydrocarbons such as xylene, alkylbenzene,methylnaphthalene and the like; alcohols such as 2-propanol, ethyleneglycol, propylene glycol, cellosolve and the like; ketones such asacetone, cyclohexanone, isophorone and the like; vegetable oils such assoybean oil, cottonseed oil and the like; aliphatic hydrocarbons,esters, dimethylsulfoxide, acetonitrile and water.

Surfactants include, for example, anionic surfactants such asalkylsulfuric acid ester salt, alkylarylsulfonic acid salt,dialkylsulfosuccinic acid salt, polyoxyethylenealkylaryletherphosphoricacid ester salt, lignin sulfonic acid salt, naphthalenesulfonatepolycondensed with formaldehyde and the like; and nonionic surfactantssuch as polyoxyethylenealkylarylether,polyoxyethylenealkylpolyoxypropyleneblockcopolymer, sorbitan fatty acidester and the like.

Another adjuvant for formulation includes, for example, water-solublepolymers such as polyvinylalcohol, polyvinylpyrrolidone and the like;Arabian gum; alginic acid and its salt thereof; polysaccharides such asCMC (carboxymethylcellulose), xanthan gum and the like; inorganicsubstances such as aluminum magnesium silicate, alumina sol and thelike; and preservatives, colorants, PAP (isopropyl acidic phosphate),stabilizing agents such as BHT and the like.

By applying the fungicidal composition of the present invention tofoliage of plants, said plants can be protected from plant diseases; andby applying the fungicidal composition of the present invention tosoils, the plants grown on said soils can be protected from plantdiseases. Namely, the fungicidal composition of the present invention isusually used for a method for controlling plant diseases comprising astep applying an effective amount of the fungicidal composition of thepresent invention to plants or soils growing the plants.

When the fungicidal composition of the present invention is applied toplants or when the fungicidal composition of the present invention isapplied to soil, the application amount thereof, which may be variedwith a kind of control-object plants, a kind of control-object diseases,an infestation level of control-object diseases, formulation types,application timings, weather conditions and the like, is usually 1 to5,000 g, preferably 5 to 1,000 g, of the compound of the presentinvention per 10,000 m².

Emulsifiable concentrate, wettable powder, flowable and the like areusually sprayed after diluted with water. In this case, theconcentration of the compound of the present invention is usually in therange of from 0.0001 to 3% by weight, preferably from 0.0005 to 1% byweight. Dust, granule and the like are usually directly applied withoutdilution.

The fungicidal composition of the present invention can be also appliedin treatment methods of seed disinfection. The methods include, forexample, a method to soak seeds of a plant in the fungicidal compositionof the present invention which prepared in 1 to 1,000 ppm in terms ofconcentration of the compound of the present invention, a method tospray or coat seeds of a plant with the fungicidal composition of thepresent invention which prepared in 1 to 1,000 ppm in terms ofconcentration of the compound of the present invention, and a method tocoat seeds of a plant with the fungicidal composition of the presentinvention which is formulated to dust.

The method for controlling plant diseases of the present invention isusually performed by applying effective amount of the fungicidalcomposition of the present invention to a plant or a soil growing theplant in which infection is predictable.

The fungicidal composition of the present invention is usually used as afungicide controlling plant diseases for agriculture or gardening, thatis, as an agent controlling plant diseases to control plant diseases onplowed fields, paddyfields, orchards, tea fields, pastures, turf and thelike.

The fungicidal composition of the present invention may be used togetherwith other fungicides, insecticides, acaricides, nematicides,herbicides, plant growth regulators and/or fertilizers.

Examples of the active ingredient of the fungicides include azolefungicidal compounds such as propiconazole, triadimenol, prochloraz,penconazole, tebuconazole, flusilazole, diniconazole, bromuconazole,epoxyconazole, difenoconazole, cyproconazole, metconazole, triflumizole,tetraconazole, myclobutanil, fenbuconazole, hexaconazole,fluquinconazole, triticonazole, bitertanol, imazalil, flutriafolandsoon;cyclic amine fungicidal compounds such as fenpropimorph, tridemorph,fenpropidin and so on; benzimidazole fungicidal compounds such ascarbendazim, benomyl, thiabendazole, thiophanate-methyl and so on;procymidone; cyprodinil; pyrimethanil; diethofencarb; thiuram;fluazinam; mancozeb; iprodione; vinclozolin; chlorothalonil; captan;mepanipyrim; fenpiclonil; fludioxonil; dichlorfluanid; folpet;kresoxim-methyl; azoxystrobin; trifloxystrobin; picoxystrobin;pyraclostrobin;N-methyl-α-methoxyimino-2-[(2,5-dimethylphenoxy)methyl]phenylacetamide;spiroxamine; quinixyfen; fenhexamide; famoxadone; fenamidone;iprovalicarb; benthiavalicarb; cyazofamid boscalid; metrafenone andcyflufenamid.

The present invention will be illustrated further in detail byproduction examples, formulation examples, test examples and the likebelow, but the present invention is not limited to these examples.

First, production examples of the compound of the present invention willbe described.

PRODUCTION EXAMPLE 1

4.00 g of5-(4-chlorophenyl)-6-methyl-4-(2,4,6-trifluorophenyl)-2H-pyridazin-3-oneand 20 ml of phosphorus oxychloride were mixed and stirred at 110° C.for 1 hour. The reaction mixture was cooled down to room temperature andconcentrated under reduced pressure. To the residue was added ethylacetate and ice water, and was separated to two layer. The organic layerwas washed sequentially with water and saturated brine, and dried overanhydrous sodium sulfate, then, concentrated under reduced pressure, toobtain 4.16 g of3-chloro-5-(4-chlorophenyl)-6-methyl-4-(2,4,6-trifluorophenyl)pyridazine(hereinafter, referred to as compound (i) of the present invention).

Compound (i) of the present invention:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.54 (3H, s), 6.63 (2H, dd, J=7.3, 8.5 Hz),7.01 (2H, d, J=8.7 Hz), 7.32 (2H, d, J=8.7 Hz)

PRODUCTION EXAMPLE 2

1.01 g of compound (i) of the present invention, 0.58 g of sodiummethoxide (28% methanol solution) and 6 ml of methanol were mixed, andstirred at room temperature for 1 day, then, at 60° C. overnight. Thereaction mixture was allowed to cool to room temperature. Water waspoured into the reaction mixture and extracted with ethyl acetate. Theorganic layer was washed with water, and dried over anhydrous sodiumsulfate, then, concentrated under reduced pressure. The residue wassubjected to silica gel column chromatography (elution solvent:hexane-ethyl acetate), to obtain 0.32 g of5-(4-chlorophenyl)-3-methoxy-6-methyl-4-(2,4,6-trifluorophenyl)pyridazine(hereinafter, referred to as compound (ii) of the present invention) and89 mg of5-(4-chlorophenyl)-4-(2,6-difluoro-4-methoxyphenyl)-3-methoxy-6-pyridazine(hereinafter, referred to as compound (iii) of the present invention),respectively.

Compound (ii) of the present invention:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.44 (3H, s), 4.11 (3H, s), 6.57 (2H, dd,J=7.3, 8.7 Hz), 7.00 (2H, d, J=8.5 Hz), 7.29 (2H, d, J=8.5 Hz)

Compound (iii) of the present invention:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.43 (3H, s), 3.75 (3H, s), 4.10 (3H, s),6.34 (2H, d, J=9.0 Hz), 7.02 (2H, d, J=8.5 Hz), 7.28 (2H, d, J=8.5 Hz)

PRODUCTION EXAMPLE 3

3.50 g of5-(4-chlorophenyl)-6-methyl-4-(2,3,6-trifluorophenyl)-2H-pyridazin-3-oneand 15 g of phosphorus oxychloride were mixed and stirred at 110° C. for1 hour. The reaction mixture was cooled down to room temperature andconcentrated under reduced pressure. To the residue was added ethylacetate and ice water, and was separated to two layer. The organic layerwas washed sequentially with water and saturated brine, and dried overanhydrous sodium sulfate, then, concentrated under reduced pressure, toobtain 3.68 g of3-chloro-5-(4-chlorophenyl)-6-methyl-4-(2,3,6-trifluorophenyl)pyridazine(hereinafter, referred to as compound (iv) of the present invention).

Compound (iv) of the present invention:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.55 (3H, s), 6.75-6.85 (1H, m), 7.03 (2H,d, J=8.4 Hz), 7.1-7.2 (1H, m), 7.32 (2H, d, J=8.4 Hz)

PRODUCTION EXAMPLE 4

185 mg of5-(4-chlorophenyl)-4-(2,6-difluoro-4-methoxyphenyl)-6-methyl-2H-pyridazin-3-oneand 5 g of phosphorus oxychloride were mixed and stirred at 110° C. for1 hour. There action mixture was allowed to cool down to roomtemperature and concentrated under reduced pressure. To the residue wasadded ethyl acetate and ice water, and separated to two layer. Theorganic layer was washed sequentially with water and saturated brine,and dried over anhydrous sodium sulfate, then, concentrated underreduced pressure. The residue was subjected to preparative thin layerchromatography (stationary phase: silica gel, developing solvent:hexane/ethyl acetate=3/1), to obtain 161 mg of3-chloro-5-(4-chlorophenyl)-4-(2,6-difluoro-4-methoxyphenyl)-6-methylpyridazine(hereinafter, referred to as compound (v) of the present invention).

Compound (v) of the present invention:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.52 (3H, s), 3.77 (3H, s), 6.38 (2H, dd,J=4.12 Hz), 7.03 (2H, d, J=8 Hz), 7.31 (2H, d, J=8 Hz)

PRODUCTION EXAMPLE 5

0.25 g of5-(4-chlorophenyl)-4-(2,6-difluoro-4-ethoxyphenyl)-6-methyl-2H-pyridazin-3-oneand 5 g of phosphorus oxychloride were mixed and stirred at 110° C. for1 hour. The reaction mixture was allowed to cool down to roomtemperature and concentrated under reduced pressure. To the residue wasadded ethyl acetate and ice water, and was separated to two layer. Theorganic layer was washed sequentially with water and saturated brine,and dried over anhydrous sodium sulfate, then, concentrated underreduced pressure. The residue was subjected to preparative thin layerchromatography (stationary phase: silica gel, developing solvent:hexane/ethyl acetate=3/1), to obtain 0.16 g of3-chloro-5-(4-chlorophenyl)-4-(2,6-difluoro-4-ethoxyphenyl)-6-methylpyridazine(hereinafter, referred to as compound (vi) of the present invention).

Compound (vi) of the present invention:

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.40 (3H, t, J=7.2 Hz), 2.52 (3H, s), 3.96(2H, q, J=7.2 Hz), 6.36 (2H, dd, J=5.2, 14.4 Hz), 7.02 (2H, d, J=8.8Hz), 7.30 (2H, d, J=8.8 Hz)

PRODUCTION EXAMPLE 6

2.09 g of5-(4-chlorophenyl)-6-methyl-4-(2,4,5-trifluorophenyl)-2H-pyridazin-3-oneand 10 g of phosphorus oxychloride were mixed and stirred at 110° C. for1 hour. There action mixture was allowed to cool down to roomtemperature and concentrated under reduced pressure. To the residue wasadded ethyl acetate and ice water, and was separated to two layer. Theorganic layer was washed sequentially with water and saturated brine,and dried over anhydrous sodium sulfate, then, concentrated underreduced pressure, to obtain 2.10 g of3-chloro-5-(4-chlorophenyl)-6-methyl-4-(2,4,5-trifluorophenyl)pyridazine(hereinafter, referred to gas compound (vii) of the present invention).

Compound (vii) of the present invention:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.53 (3H, s), 6.8-6.95 (2H), 6.95-7.05 (2H,br), 7.33 (2H, d, J=8.8 Hz)

PRODUCTION EXAMPLE 7

1.80 g of5-(4-chlorophenyl)-6-methyl-4-(2,3,5-trifluorophenyl)-2H-pyridazin-3-oneand 10 g of phosphorus oxychloride were mixed and stirred at 110° C. for1 hour. The reaction mixture was allowed to cool down to roomtemperature and concentrated under reduced pressure. To the residue wasadded ethyl acetate and ice water, and was separated to two layer. Theorganic layer was washed sequentially with water and saturated brine,and dried over anhydrous sodium sulfate, then, concentrated underreduced pressure, to obtain 1.83 g of3-chloro-5-(4-chlorophenyl)-6-methyl-4-(2,3,5-trifluorophenyl)pyridazine(hereinafter, referred to as compound (viii) of the present invention).

Compound (viii) of the present invention:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.54 (3H, s), 6.5-6.55 (1H, m), 6.85-6.95(1H, m), 6.95-7.05 (2H, br), 7.34 (2H, d, J=8.4 Hz)

PRODUCTION EXAMPLE 8

6.0 g of5-(4-chlorophenyl)-4-(2,6-difluoro-4-nitrophenyl)-6-methyl-2H-pyridazin-3-oneand 30 g of phosphorus oxychloride were mixed and stirred at 110° C. for1 hour. There action mixture was allowed to cool down to roomtemperature and concentrated under reduced pressure. To the residue wasadded ethyl acetate and ice water, and was separated to two layer. Theorganic layer was washed sequentially with water and saturated brine,and dried over anhydrous sodium sulfate, then, concentrated underreduced pressure, to obtain 6.15 g of3-chloro-5-(4-chlorophenyl)-4-(2,6-difluoro-4-nitrophenyl)-6-methylpyridazine(hereinafter, referred to as compound (ix) of the present invention).

Compound (ix) of the present invention:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.57 (3H, s), 7.03 (2H, d, J=8.4 Hz), 7.33(2H, d, J=8.4 Hz), 7.75-7.8 (2H, m)

PRODUCTION EXAMPLE 9

1.33 g of4-(3-chloro-2,6-difluorophenyl)-5-(4-chlorophenyl)-6-methyl-2H-pyridazin-3-oneand 10 g of phosphorus oxychloride were mixed and stirred at 110° C. for1 hour. There action mixture was allowed to cool down to roomtemperature and concentrated under reduced pressure. To the residue wasadded ethyl acetate and ice water, and was separated to two layer. Theorganic layer was washed sequentially with water and saturated brine,and dried over anhydrous sodium sulfate, then, concentrated underreduced pressure, to obtain 1.33 g of3-chloro-4-(3-chloro-2,6-difluorophenyl)-5-(4-chlorophenyl)-6-methylpyridazine(hereinafter, referred to as compound (x) of the present invention).

Compound (x) of the present invention:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.56 (3H, s), 6.8-6.85 (1H, m), 7.02 (2H,d, J=8.4 Hz), 7.32 (2H, d, J=8.4 Hz), 7.35-7.4 (1H, m)

PRODUCTION EXAMPLE 10

To a mixture of 323 mg of copper (II) chloride (CuCl₂), 309 mg oftert-butyl nitrite and 13 ml of acetonitrile was added 732 mg of4-(4-amino-2,6-difluorophenyl)-3-cholor-5-(4-cholorphenyl)-6-methylpyridazineportion-wise under ice-cooling. Thereafter, the reaction mixture wasstirred at room temperature for 2 hours. Then, the reaction mixture waspoured into a mixture of ice and dilute hydrochloric acid, and extractedwith ethyl acetate. The organic layer was washed sequentially withsodium bicarbonate water and saturated brine, and dried over anhydrousmagnesium sulfate then concentrated. The residue was subjected to silicagel column chromatography (elution solvent; hexane: ethyl acetate=7:1),to obtain 0.62 g of3-chloro-4-(4-chloro-2,6-difluorophenyl)-5-(4-chlorophenyl)-6-methylpyridazine(hereinafter, referred to as compound (xi) of the present invention).

Compound (xi) of the present invention

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.54 (3H, s), 6.90 (2H, dd, J=4.8, 11.6Hz), 7.02 (2H, d, J=8.4 Hz), 7.33 (2H, d, J=8.4 Hz)

PRODUCTION EXAMPLE 11

3.49 g of5-(4-chlorophenyl)-4-(2,3-difluorophenyl)-6-methyl-2H-pyridazin-3-oneand 10 g of phosphorus oxychloride were mixed and stirred at 110° C. for1 hour. The reaction mixture was allowed to cool down to roomtemperature and concentrated under reduced pressure. To the residue wasadded ethyl acetate and ice water, and was separated to two layer. Theorganic layer was washed sequentially with water and saturated brine,and dried over anhydrous sodium sulfate, then, concentrated underreduced pressure, to obtain 3.66 g of3-chloro-5-(4-chlorophenyl)-4-(2,3-difluorophenyl)-6-methylpyridazine(hereinafter, referred to as compound (xii) of the present invention).

Compound (xii) of the present invention:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.54 (3H, s), 6.7-6.8 (1H, m), 6.95-7.1(3H), 7.1-7.2 (1H, m), 7.29 (2H, d, J=8.4 Hz)

PRODUCTION EXAMPLE 12

2.86 g of5-(4-chlorophenyl)-4-(2,5-difluorophenyl)-6-methyl-2H-pyridazin-3-oneand 6.5 g of phosphorus oxychloride were mixed and stirred at 110° C.for 1 hour. The reaction mixture was allowed to cool down to roomtemperature and concentrated under reduced pressure. To the residue wasadded ethyl acetate and ice water, and was separated to two layer. Theorganic layer was washed sequentially with water and saturated brine,and dried over anhydrous sodium sulfate, then, concentrated. The residuewas subjected to silica gel column chromatography (elution solvent;hexane:ethyl acetate=3:1, to obtain 2.89 g of3-chloro-5-(4-chlorophenyl)-4-(2,5-difluorophenyl)-6-methyl pyridazine(hereinafter, referred to as compound (xiii) of the present invention).

Compound (xiii) of the present invention:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.54 (3H, s), 6.7-6.75 (1H, m), 6.95-7.05(4H), 7.33 (2H, d, J=8.8 Hz)

PRODUCTION EXAMPLE 13

7.61 g of5-(4-chlorophenyl)-4-(2,6-difluoropheyl)-6-methyl-2H-pyridazin-3-one and40 ml of phosphorus oxychloride were mixed and stirred at 110° C. for 4hours. There action mixture was allowed to cool down to room temperatureand concentrated under reduced pressure. To the residue was added ethylacetate and ice water, and was separated to two layer. The organic layerwas washed sequentially with water and saturated brine, and dried overanhydrous sodium sulfate, then, concentrated under reduced pressure, toobtain 8.52 g of3-chloro-5-(4-chlorophenyl)-4-(2,6-difluorophenyl)-6-methyl pyridazine(hereinafter, referred to as compound (xiv) of the present invention).

Compound (xiv) of the present invention:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.54 (3H, s), 6.75-6.85 (2H, m), 6.9-7.0(3H), 7.30 (2H, d, J=8.8 Hz)

PRODUCTION EXAMPLE 14

1.20 g of5-(4-chlorophenyl)-4-(2,4-difluorophenyl)-6-methyl-2H-pyridazin-3-oneand 10 g of phosphorus oxychloride were mixed and stirred at 110° C. for1 hour. The reaction mixture was allowed to cool down to roomtemperature and concentrated under reduced pressure. To the residue wasadded ethyl acetate and ice water, and was separated to two layer. Theorganic layer was washed sequentially with water and saturated brine,and dried over anhydrous sodium sulfate, then, concentrated underreduced pressure, to obtain 1.22 g of3-chloro-5-(4-chlorophenyl)-4-(2,4-difluorophenyl)-6-methylpyridazine(hereinafter, referred to as compound (xv) of the present invention).

Compound (xv) of the present invention:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.53 (3H, s), 6.75-6.85 (2H), 6.9-7.0 (3H),7.29 (2H, d, J=8.8 Hz)

PRODUCTION EXAMPLE 15

2.16 g of4-(2-chloro-6-fluorophenyl)-5-(4-chlorophenyl)-6-methyl-2H-pyridazin-3-oneand 10 g of phosphorus oxychloride were mixed and stirred at 110° C. for1 hour. There action mixture was allowed to cool down to roomtemperature and concentrated under reduced pressure. To the residue wasadded ethyl acetate and ice water, and was separated to two layer. Theorganic layer was washed sequentially with water and saturated brine,and dried over anhydrous sodium sulfate, then, concentrated underreduced pressure, to obtain 2.21 g of3-chloro-4-(2-chloro-6-fluorophenyl)-5-(4-chlorophenyl)-6-methylpyridazine(hereinafter, referred to as compound (xvi) of the present invention).

Compound (xvi) of the present invention:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.54 (3H, s), 6.9-7.0 (1H, m), 7.07 (2H, d,J=8.8 Hz), 7.17 (1H, d, J=8.0 Hz), 7.2-7.3 (3H)

PRODUCTION EXAMPLE 16

1.95 g of5-(4-chlorophenyl)-4-(2-fluorophenyl)-6-methyl-2H-pyridazin-3-one and 10g of phosphorus oxychloride were mixed and stirred at 110° C. for 1hour. The reaction mixture was allowed to cool down to room temperatureand concentrated under reduced pressure. To the residue was added ethylacetate and ice water, and was separated to two layer. The organic layerwas washed sequentially with water and saturated brine, and dried overanhydrous sodium sulfate, then, concentrated under reduced pressure, toobtain

1.96 g of3-chloro-5-(4-chlorophenyl)-4-(2-fluorophenyl)-6-methylpyridazine(hereinafter, referred to as compound (xvii) of the present invention).

Compound (xvii) of the present invention:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.53 (3H, s), 6.95-7.1 (5H), 7.25-7.35 (3H)

PRODUCTION EXAMPLE 17

2.36 g of5-(4-fluorophenyl)-6-methyl-4-(2,4,6-trifluorophenyl)-2H-pyridazin-3-oneand 10 g of phosphorus oxychloride were mixed and stirred at 110° C. for1 hour. The reaction mixture was allowed to cool down to roomtemperature and concentrated under reduced pressure. To the residue wasadded ethyl acetate and ice water, and was separated to two layer. Theorganic layer was washed sequentially with water and saturated brine,and dried over anhydrous sodium sulfate, then, concentrated underreduced pressure, to obtain 2.34 g of3-chloro-5-(4-fluorophenyl)-6-methyl-4-(2,4,6-trifluorophenyl)pyridazine(hereinafter, referred to as compound (xviii) of the present invention).

Compound (xviii) of the present invention:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.54 (3H, s), 6.6-6.65 (2H, m), 7.0-7.1(4H, m)

PRODUCTION EXAMPLE 18

2.06 g of5-(4-methoxyphenyl)-6-methyl-4-(2,4,6-trifluorophenyl)-2H-pyridazin-3-oneand 10 g of phosphorus oxychloride were mixed and stirred at 110° C. for1 hour. There action mixture was allowed to cool down to roomtemperature and concentrated under reduced pressure. To the residue wasadded ethyl acetate and ice water, and was separated to two layer. Theorganic layer was washed sequentially with water and saturated brine,and dried over anhydrous sodium sulfate, then, concentrated underreduced pressure, to obtain 2.14 g of3-chloro-5-(4-methoxyphenyl)-6-methyl-4-(2,4,6-trifluorophenyl)pyridazine(hereinafter, referred to as compound (xix) of the present invention).

Compound (xix) of the present invention:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.55 (3H, s), 3.80 (3H, s), 6.55-6.65 (2H,m), 6.83 (2H, d, J=8.4 Hz), 6.98 (2H, d, J=8.4 Hz)

PRODUCTION EXAMPLE 19

2.34 g of5-(3-chlorophenyl)-6-methyl-4-(2,4,6-trifluorophenyl)-2H-pyridazin-3-oneand 10 g of phosphorus oxychloride were mixed and stirred at 110° C. for1 hour. There action mixture was allowed to cool down to roomtemperature and concentrated under reduced pressure. To the residue wasadded ethyl acetate and ice water, and was separated to two layer. Theorganic layer was washed sequentially with water and saturated brine,and dried over anhydrous sodium sulfate, then, concentrated underreduced pressure, to obtain 2.39 g of3-chloro-5-(3-chlorophenyl)-6-methyl-4-(2,4,6-trifluorophenyl)pyridazine(hereinafter, referred to as compound (xx) of the present invention).

Compound (xx) of the present invention:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.55 (3H, s), 6.6-6.7 (2H, br), 6.96 (1H,d, J=7.8 Hz), 7.09 (1H), 7.3-7.35 (2H)

PRODUCTION EXAMPLE 20

1.67 g of 6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)-2H-pyridazin-3-oneand 10 g of phosphorus oxychloride were mixed and stirred at 110° C. for1 hour. The reaction mixture was allowed to cool down to roomtemperature and concentrated under reduced pressure. To the residue wasadded ethyl acetate and ice water, and was separated to two layer. Theorganic layer was washed sequentially with water and saturated brine,and dried over anhydrous sodium sulfate, then, concentrated underreduced pressure, to obtain 1.74 g of3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine(hereinafter, referred to as compound (xxi) of the present invention).

Compound (xxi) of the present invention:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.54 (3H, s), 6.55-6.65 (2H, m), 7.05-7.1(2H), 7.3-7.35 (3H)

PRODUCTION EXAMPLE 21

19.77 g of6-methyl-5-(4-methylphenyl)-4-(2,4,6-trifluorophenyl)-2H-pyridazin-3-oneand 100 ml of phosphorus oxychloride were mixed and stirred at 110° C.for 1 hour. There action mixture was allowed to cool down to roomtemperature and concentrated under reduced pressure. To the residue wasadded chloroform and ice water, and was separated to two layer. Theorganic layer was washed sequentially with water and saturated brine,and dried over anhydrous sodium sulfate, then, concentrated underreduced pressure, to obtain 19.90 g of3-chloro-6-methyl-5-(4-methylphenyl)-4-(2,4,6-trifluorophenyl)pyridazine(hereinafter, referred to as compound (xxii) of the present invention).

Compound (xxii) of the present invention:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.32 (3H, s), 2.55 (3H, s), 6.55-6.65 (2H,m) 6.94 (2H, d, J=8.4 Hz), 7.12 (2H, d, J=8.4 Hz)

PRODUCTION EXAMPLE 22

1.75 g of5-(3,4-dichlorophenyl)-6-methyl-4-(2,4,6-trifluorophenyl)-2H-pyridazin-3-oneand 6 ml of phosphorus oxychloride were mixed and stirred at 110° C. for1 hour. There action mixture was allowed to cool down to roomtemperature and concentrated under reduced pressure. To the residue wasadded ethyl acetate and ice water, and was separated to two layer. Theorganic layer was washed sequentially with water and saturated brine,and dried over anhydrous sodium sulfate, then, concentrated underreduced pressure to obtain 1.80 g of3-chloro-5-(3,4-dichlorophenyl)-6-methyl-4-(2,4,6-trifluorophenyl)pyridazine(hereinafter, referred to as compound (xxiii) of the present invention).

Compound (xxiii) of the present invention:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.55 (3H, s), 6.67 (2H, br t), 6.93 (1H,dd), 7.20 (1H, d), 7.43 (1H, d)

PRODUCTION EXAMPLE 23

2.43 g of6-methyl-5-(4-trifluoromethylphenyl)-4-(2,4,6-trifluorophenyl)-2H-pyridazin-3-oneand 10 g of phosphorus oxychloride were mixed and stirred at 110° C. for1 hour. The reaction mixture was allowed to cool down to roomtemperature and concentrated under reduced pressure. To the residue wasadded ethyl acetate and ice water, and was separated to two layer. Theorganic layer was washed sequentially with water and saturated brine,and dried over anhydrous sodium sulfate, then, concentrated underreduced pressure, to obtain 2.50 g of3-chloro-6-methyl-5-(4-trifluoromethylphenyl)-4-(2,4,6-trifluorophenyl)pyridazine(hereinafter, referred to as compound (xxiv) of the present invention).

Compound (xxiv) of the present invention:

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.53 (3H, s), 6.6-6.7 (2H, m), 7.23 (2H, d,J=8.0 Hz), 7.62 (2H, d, J=8.0 Hz)

Next, reference production examples for production of intermediates ofthe compounds of the present invention are shown.

REFERENCE PRODUCTION EXAMPLE 1

To a mixture of 10.12 g of 4-chloropropiophenone, 0.1 ml of hydrobromicacid (48% aqueous solution) and 60 ml of acetic acid was added 3.1 ml ofbromine at 0° C. under a nitrogen atmosphere, and stirred at roomtemperature for 1 hour. Thereafter, the reaction mixture wasconcentrated under reduced pressure, to obtain 14.34 g of2-bromo-4′-chloropropiophenone.

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.90 (3H, d, J=6.5 Hz), 5.22 (1H, q, J=6.5Hz), 7.46 (2H, d, J=8.7 Hz), 7.97 (2H, d, J=8.7 Hz)

REFERENCE PRODUCTION EXAMPLE 2

14.32 g of 2-bromo-4′-chloropropiophenone, 12.08 g of2,4,6-trifluorophenylacetic acid, 170 ml of acetonitrile and 6.43 g oftriethylamine were mixed and stirred at room temperature for overnight.To this mixture was added 210 ml of acetonitrile at room temperature,then, the mixture was cooled to 0° C., and 21.5 g of DBU was added over25 minutes. The mixture was stirred for 2 hours at 0° C. Thereafter, airwas blown into the resultant mixture at room temperature while stirringfor 4.5 hours. To the reaction mixture was added 1 mol/L hydrochloricacid, and extracted with ethyl acetate. The organic layer was washedsequentially with saturated sodium bicarbonate aqueous solution andsaturated brine, and dried over anhydrous magnesium sulfate, then,concentrated under reduced pressure. The resulting residue was subjectedto silica gel chromatography to obtain 17.89 g of4-(4-chlorophenyl)-5-hydroxy-5-methyl-3-(2,4,6-trifluorophenyl)-2(5H)-furanone.

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.76 (3H, s), 4.20 (1H, br), 6.63 (1 H,br), 6.80 (1H, br), 7.33 (2H, d, J=8.7 Hz), 7.48 (2H, d, J=8.7 Hz)

Next, compounds produced in a similar manner as this production exampleand their NMR data are shown.

-   4-(4-chlorophenyl)-5-hydroxy-5-methyl-3-(2,3,6-trifluorophenyl)-2(5H)-furanone;

¹H-NMR (DMSO-d6, TMS) δ (ppm): 1.66 (3H, s), 7.15-7.4 (1H, br), 7.51(4H, s), 7.6-7.7 (1H, m), 8.39 (1H, s)

-   4-(4-chlorophenyl)-5-hydroxy-5-methyl-3-(2,4,5-trifluorophenyl)-2(5H)-furanone;

¹H-NMR (DMSO-d6, TMS) δ (ppm): 1.61 (3H, s), 7.4-7.65 (6H), 8.23 (1H,br)

-   4-(4-chlorophenyl)-5-hydroxy-5-methyl-3-(2,3,5-trifluorophenyl)-2(5H)-furanone;

¹H-NMR (DMSO-d6, TMS) δ (ppm): 1.62 (3H, s), 7.1-7.2 (1H, br), 7.45-7.55(4H), 7.6-7.7 (1H, br), 8.22 (1H, s)

-   4-(4-chlorophenyl)-3-(2,6-difluoro-4-nitrophenyl)-5-hydroxy-5-methyl-2(5)-furanone;

¹H-NMR (DMSO-d6, TMS) δ (ppm): 1.67 (3H, s), 7.45-7.55 (4H), 8.05-8.3(2H, br), 8.47 (1H, s)

-   3-(3-chloro-2,6-difluorophenyl)-4-(4-chlorophenyl)-5-hydroxy-5-methyl-2(5H)-furanone;

¹H-NMR (DMSO-d6, TMS) δ (ppm): 1.65 (3H, s), 7.28 (1H, br), 7.50 (4H,s), 7.78 (1H, br dd, J=8.8, 10.4 Hz), 8.40 (1H, br s)

-   4-(4-chlorophenyl)-3-(2,3-difluorophenyl)-5-hydroxy-5-methyl-2(5)-furanone;

¹H-NMR (DMSO-d6, TMS) δ (ppm): 1.63 (3H, s), 7.15-7.25 (1H, m),7.25-7.35 (1H, m), 7.4-7.6 (5H), 8.18 (1H, s)

-   4-(4-chlorophenyl)-3-(2,5-difluorophenyl)-5-hydroxy-5-methyl-2(5)-furanone;

¹H-NMR (DMSO-d6, TMS) δ (ppm): 1.60 (3H, s), 7.15-7.55 (7H), 8.15 (1H,s)

-   4-(4-chlorophenyl)-3-(2,6-difluorophenyl)-5-hydroxy-5-methyl-2(5)-furanone;

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.73 (3H, s), 4.2-4.4 (1H, br), 6.75-6.85(1H, m), 6.9-7.0 (1H, m), 7.31 (2H, d, J=8.8 Hz), 7.3-7.4 (1H, m), 7.45(2H, d, J=8.8 Hz)

-   4-(4-chlorophenyl)-3-(2,4-difluorophenyl)-5-hydroxy-5-methyl-2(5H)-furanone;

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.74 (3H, s), 3.83 (1H, s), 6.75-6.85 (1H,m), 6.9-7.0 (1H, m), 7.32 (2H, d, J=8.8 Hz), 7.35-7.45 (1H, m), 7.46(2H, d, J=8.8 Hz)

-   4-(4-chlorophenyl)-3-(2-fluorophenyl)-5-hydroxy-5-methyl-2(5H)-furanone;

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.73 (3H, s), 4.37 (1H, s), 7.04 (1H, t,J=8.8 Hz), 7.17 (1H, t, J=7.8 Hz), 7.28 (2H, d, J=8.4 Hz), 7.3-7.4 (2H),7.46 (2H, d, J=8.4 Hz)

-   4-(4-fluorophenyl)-5-hydroxy-5-methyl-3-(2,4,6-trifluoropohenyl)-2(5H)-furanone;

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.77 (3H, s), 4.42 (1H, br s), 6.55-6.95(2H), 7.0-7.1 (2H, m), 7.5-7.6 (2H, m)

-   5-hydroxy-4-(4-methoxyphenyl)-5-methyl-3-(2,4,6-trifluorophenyl)-2(5H)-furanone;

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.80 (3H, s), 3.82 (3H, s), 4.16 (1H, br),6.6-6.7 (1H, br), 6.75-6.85 (1H, m), 6.76 (2H, d, J=8.8 Hz), 7.54 (2H,d, J=8.8 Hz)

-   4-(3-chlorophenyl)-5-hydroxy-5-methyl-3-(2,4,6-trifluorophenyl)-2(5H)-furanone;

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.77 (3H, s), 4.27 (1H, br s), 6.65-6.8(2H), 7.25-7.4 (3H), 7.57 (1H)

-   5-hydroxy-5-methyl-4-phenyl-3-(2,4,6-trifluoropohenyl)-2(5H)-furanone;

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.79 (3H, s), 4.17 (1H, br), 6.65-6.8 (2H),7.3-7.5 (3H), 7.5-7.6 (2H)

-   5-hydroxy-5-methyl-4-(4-methylphenyl)-3-(2,4,6-trifluorophenyl)-2(5H)-furanone;

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.80 (3H, s), 2.30 (3H, s), 3.93 (1H, br),6.6-6.7 (1H, br), 6.75-6.9 (1H, br), 7.16 (2H, d, J=8 Hz), 7.44 (2H, d,J=8 Hz)

-   4-(3,4-dichlorophenyl)-5-hydroxy-5-methyl-3-(2,4,6-trifluorophenyl)-2(5H)-furanone;

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.76 (3H, s), 4.4-4.8 (1H, br), 6.65 (1H,br), 6.8 (1H, br), 7.31 (1H, dd, J=2, 8.4 Hz), 7.42 (1H, d, J=8.4 Hz),7.70 (1H, d, J=2 Hz)

-   5-hydroxy-5-methyl-4-(4-trifluoromethylphenyl)-3-(2,4,6-trifluorophenyl)-2(5H)-furanone;

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.78 (3H, s), 4.05 (1H, br s), 6.55-6.9(2H), 6.6-6.7 (4H)

REFERENCE PRODUCTION EXAMPLE 3

17.03 g of4-(4-chlorophenyl)-5-hydroxy-5-methyl-3-(2,4,6-trifluorophenyl)-2(5H)-furanone,2.64 g of hydrazine monohydrate and 240 ml of 1-butanol were mixed, andstirred at 90° C. for 3 hours. Then, the reaction mixture was cooled to0° C. The resulting solid was collected by filtration. The collectedsolid was washed using hexane and t-butyl methyl ether, and dried underreduced pressure to obtain 6.99 g of5-(4-chlorophenyl)-6-methyl-4-(2,4,6-trifluorophenyl)-2H-pyridazin-3-one.

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.11 (3H, s), 6.57 (2H, dd, J=7.3, 8.7 Hz),7.03 (2H, d, J=8.3 Hz), 7.30 (2H, d, J=8.3 Hz), 11.04 (1H, s)

Next, compounds produced in a similar manner as this production exampleand their NMR data are shown.

-   5-(4-chlorophenyl)-6-methyl-4-(2,3,6-trifluorophenyl)-2H-pyridazin-3-one

¹H-NMR (DMSO-d6, TMS) δ (ppm): 2.06 (3H, s), 7.05 (1H, br), 7.19 (2H,br), 7.35-7.45 (3H)

-   5-(4-chlorophenyl)-6-methyl-4-(2,4,5-trifluorophenyl)-2H-pyridazin-3-one

¹H-NMR (DMSO-d6, TMS) δ (ppm): 2.02 (3H, s), 7.10-7.45 (6H), 13.23 (1H,s)

-   5-(4-chlorophenyl)-6-methyl-4-(2,3,5-trifluorophenyl)-2H-pyridazin-3-one

¹H-NMR (DMSO-d6, TMS) δ (ppm): 2.03 (3H, s), 6.93 (1H, br), 7.17 (1H,br), 7.33 (1H, br), 7.35-7.5 (3H), 13.28 (1H, s)

-   5-(4-chlorophenyl)-4-(2,6-difluoro-4-nitrophenyl)-6-methyl-2H-pyridazin-3-one

¹H-NMR (DMSO-d6, TMS) δ (ppm): 2.07 (3H, s), 7.20 (2H, d, J=8 Hz), 7.40(2H, d, J=8 Hz), 7.95-8.05 (2H, m)

-   4-(3-chloro-2,6-difluorophenyl)-5-(4-chlorophenyl)-6-methyl-2H-pyridazin-3-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.12 (3H, s), 6.75-6.8 (1H, m), 7.04 (2H,d, J=8.8 Hz), 7.25-7.35 (3H), 11.86 (1H, br s)

-   5-(4-chlorophenyl)-4-(2,3-difluorophenyl)-6-methyl-2H-pyridazin-3-one

¹H-NMR (DMSO-d6, TMS) δ (ppm): 2.02 (3H, s), 6.85-6.95 (1H m), 7.0-7.15(2H), 7.25-7.45 (4H), 13.22 (1H, s)

-   5-(4-chlorophenyl)-4-(2,5-difluorophenyl)-6-methyl-2H-pyridazin-3-one

¹H-NMR (DMSO-d6, TMS) δ (ppm): 2.01 (3H, s), 7.0-7.4 (7H), 13.19 (1H, s)

-   5-(4-chlorophenyl)-4-(2,6-difluorophenyl)-6-methyl-2H-pyridazin-3-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.11 (3H, s), 6.65-6.8 (2H), 6.9-7.1 (3H),7.25-7.35 (2H), 11.24 (1H, br)

-   5-(4-chlorophenyl)-4-(2,4-difluorophenyl)-6-methyl-2H-pyridazin-3-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.11 (3H, s), 6.65-6.8 (2H), 6.95 (1H, br),6.95-7.1 (2H), 7.2-7.35 (2H), 11.82 (1H, br s)

-   4-(2-chloro-6-fluorophenyl)-5-(4-chlorophenyl)-6-methyl-2H-pyridazin-3-one

¹H-NMR (CDCl₃ (containing one drop of DMSO-D6), TMS) δ (ppm): 2.11 and2.12 (total 3H, each s), 6.85-6.9 (1H, m), 7.05-7.35 (6H), 12.37 (1H, brs)

-   5-(4-chlorophenyl)-4-(2-fluorophenyl)-6-methyl-2H-pyridazin-3-one

¹H-NMR (CDCl₃ (containing one drop of DMSO-D6), TMS) δ (ppm): 2.11 (3H,s), 6.9-7.1 (5H), 7.2-7.3 (3H), 12.09 (1H, br s)

-   5-(4-fluorophenyl)-6-methyl-4-(2,4,6-trifluorophenyl)-2H-pyridazin-3-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.12 (3H, s), 6.5-6.6 (2H, m), 6.95-7.1(4H), 11.57 (1H, br s)

-   5-(4-methoxyphenyl)-6-methyl-4-(2,4,6-trifluorophenyl)2H-pyridazin-3-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.14 (3H, s), 3.79 (3H, s), 6.5-6.6 (2H,m), 6.82 (2H, d, J=8.8 Hz), 7.00 (2H, d, J=8.8 Hz), 10.85 (1H, br s)

-   5-(3-chlorophenyl)-6-methyl-4-(2,4,6-trifluorophenyl)-2H-pyridazin-3-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.13 (3H, s), 6.5-6.65 (2H, br), 6.98 (2H,d, J=7.2 Hz), 7.11 (1H, s), 7.25-7.35 (2H), 11.97 (1H, br s)

-   6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)-2H-pyridazin-3-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.12 (3H, s), 6.45-6.55 (2H, m), 7.05-7.1(2H), 7.25-7.35 (3H), 11.93 (1H, br s)

-   6-methyl-5-(4-methylphenyl)-4-(2,4,6-trifluorophenyl)-2H-pyridazin-3-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.12 (3H, s), 2.31 (3H, s), 6.5-6.6 (2H,m), 6.96 (2H, d, J=8 Hz), 7.10 (2H, d, J=8 Hz), 10.68 (1H, br s)

-   5-(3,4-dichlorophenyl)-6-methyl-4-(2,4,6-trifluorophenyl)-2H-pyridazin-3-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.13 (3H, s), 6.61 (1H, br t), 6.94 (1H,dd, J=2, 8.4 Hz), 7.22 (1H, d, J=2 Hz), 7.41 (1H, d, J=8.4 Hz), 10.76(1H, br s)

-   6-methyl-5-(4-trifluoromethylphenyl)-4-(2,4,6-trifluorophenyl)-2H-pyridazin-3-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.10 (3H, s), 6.57 (2H, dd, J=7.2, 8.8 Hz),7.25 (2H, d, J=8.0 Hz), 7.60 (2H, d, J=8.0 Hz), 11.13 (1H, br s)

REFERENCE PRODUCTION EXAMPLE 4

0.35 g of5-(4-chlorophenyl)-6-methyl-4-(2,4,6-trifluorophenyl)-2H-pyridazin-3-one,0.96 g of sodium methoxide (28% methanol solution) and 6 ml of methanolwere mixed and stirred for 14 hours under reflux with heating. Next, tothe reaction mixture was added 0.96 g of sodium methoxide (28% methanolsolution), and stirred for 9 hours under reflux with heating. Thereaction mixture was cooled to room temperature. Water was added to thereaction mixture, and extracted with ethyl acetate. The organic layerwas washed with water, and dried over anhydrous magnesium sulfate, then;concentrated under reduced pressure. The residue was subjected to silicagel column chromatography (elution solvent: hexane+tert-butyl methylether), to obtain 0.25 g of5-(4-chlorophenyl)-4-(2,6-difluoro-4-methoxyphenyl)-6-methyl-2H-pyridazin-3-one.

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.11 (3H, s), 3.73 (3H, s), 6.34 (2H, dd,J=4.12 Hz), 7.04 (2H, d, J=12 Hz), 7.29 (2H, d, J=12 Hz), 11.57 (1H, brs)

Next, compounds produced in a similar manner as this production exampleand their NMR data are shown.

-   5-(4-chlorophenyl)-4-(2,6-difluoro-4-ethoxyphenyl)-6-methyl-2H-pyridazin-3-one

¹H-NMR (CDCl₃, TMS) δ (ppm): 1.37 (3H, t, J=7.2 Hz), 2.10 (3H, s), 3.93(2H, q, J=7.2 Hz), 6.32 (2H, dd, J=5.2, 14.4 Hz), 7.04 (2H, d, J=8.8Hz), 7.28 (2H, d, J=8.8 Hz), 11.46 (1H, br s)

REFERENCE PRODUCTION EXAMPLE 5

A mixture of 3.91 g of iron (powder), 60 ml of acetic acid and 60 ml ofwater was stirred for 0.5 hours at 70 to 80° C. Onto this mixture wasdropped an ethyl acetate (120 ml) solution of 5.44 g of the compound(ix) of the present invention at 70 to 80° C. over 40 minutes.Thereafter, the reaction mixture was filtrated through celite. Thefiltrate was separated to two layer. The organic layer was washedsequentially with saturated brine, saturated sodium bicarbonate water (3times) and saturatedbrine, and dried over anhydrous magnesium sulfate,then, concentrated under reduced pressured to obtain 4.98 g of4-(4-amino-2,6-difluorophenyl)-3-chloro-5-(4-chlorophenyl)-6-methylpyridazine.

¹H-NMR (CDCl₃, TMS) δ (ppm): 2.51 (3H, s), 4.00 (2H, br s), 6.05-6.15(2H, m), 7.02 (2H, d, J=8.4 Hz), 7.31 (2H, d, J=8.4 Hz)

Next, Formulation examples are shown. Part means part by weight.

FORMULATION EXAMPLE 1

Fifty parts of each of compounds (i) to (xxiv) of the present invention,3 parts of calcium ligninsulfonate, 2 parts of magnesium laurylsulfateand 45 parts of synthetic hydrated silica are pulverized and mixed wellto give wettable powders of each compound.

FORMULATION EXAMPLE 2

Twenty parts of each of compounds (i) to (xxiv) of the present inventionand 1.5 parts of sorbitan trioleate are mixed with 28.5 parts of anaqueous solution containing 2 parts of polyvinyl alcohol, andwet-pulverized finely. To the obtained mixture, 40 parts of an aqueoussolution containing 0.05 part of xanthan gum and 0.1 part of aluminummagnesium silicate is added and further 10 parts of propylene glycol areadded to give a flowable of each compound.

FORMULATION EXAMPLE 3

Two parts of each of compounds (i) to (xxiv) of the present invention,88 parts of kaolin clay and 10 parts of talc are pulverized and mixedwell to give a dust of each compound.

FORMULATION EXAMPLE 4

Five parts of each of compounds (i) to (xxiv) of the present invention,14 parts of polyoxyethylenestyryl phenyl ether, 6 parts of calciumdodecylbenzenesulfonate and 75 parts of xylene are mixed well to give anemulsifiable concentrate of each compound.

FORMULATION EXAMPLE 5

Two parts of each of compounds (i) to (xxiv) of the present invention, 1part of synthetic hydrated silica, 2 parts of calcium ligninsulfonate,30 parts of bentonite and 65 parts of kaolin clay are pulverized andmixed well, and water is added thereto and kneeded, granulated and driedto give a granule of each compound.

FORMULATION EXAMPLE 6

Ten parts of each of the compounds (i) to (xxiv) of present invention,35 parts of white carbon containing 50% by weight of ammoniumpolyoxyethylenealkyl ether sulfate and 55 parts of water are mixed andwet pulverized finely to give a formulation of each compound.

Next, a fact that the compound of the present invention is effective forcontrolling plant diseases is shown by test examples.

TEST EXAMPLE 1

A plastic pot was filled with sandy loam, cucumber (cultivar: SagamiHanjiro) was sowed, and grown in a greenhouse for 10 days. Each of thecompounds (i) to (xxiv) of the present invention was formulatedaccording to Formulation Example 6, then, diluted with water to aconcentration of 500 ppm. Each of the resulting diluted solutions wassprayed on stems and leaves so as to sufficiently adhere to the surfaceof cucumber cotyledones. After spraying, the plant was air-dried, and aPDA medium containing spores of Botrytis cinerea was placed on thesurface of cucumber cotyledones. Then, the cucumber was left under humidcondition at 12° C. for 5 days. Thereafter, the lesion area of the plantwas visually observed. As a result, the lesion area of the cucumbertreated with the compounds (i) to (xxiv) of the present invention was10% or less of the lesion area of non-treated cucumber.

TEST EXAMPLE 2

A plastic pot was filled with sandy loam, paddy (cultivar: NihonBare)was sowed, and grown in a greenhouse for 15 days. Each of the compounds(i) to (xxiv) of the present invention was formulated according toFormulation Example 6, then, diluted with water to a concentration of500 ppm. Each of the resulting diluted solutions was sprayed on stem andleaves so as to sufficiently adhere to the surface of the paddy leaves.After spraying, the plant was air-dried. Plastic pots containing plantedpaddy affected by Pyricularia oryzae were placed around the plastic potof paddy, and this condition was left under humid condition at 22° C.for 6 days. Thereafter, a controlling effect was checked. As a result,the lesion area of the paddy treated with the compounds (i) to (xxiv) ofthe present invention was 10% or less of the lesion area of non-treatedpaddy.

TEST EXAMPLE 3

A plastic pot was filled with sandy loam, Japanese radish (cultivar:Wase 40 nichi) was sowed, and grown in a greenhouse for 5 days. Each ofthe compounds (i) to (xxiv) of the present invention was formulatedaccording to Formulation Example 6, then, diluted with water to aconcentration of 500 ppm. Each of the resulting diluted solutions wassprayed on stem and leaves so as to sufficiently adhere to the radish.After spraying, the plant was air-dried, and inoculated with spores ofAlternaria brassicicola. Then, this radish was left under humidcondition at 23° C. overnight, further, left in a greenhouse for 3 days.Thereafter, a controlling effect was checked. As a result, the lesionarea of the radish treated with the compounds (i) to (xxiv) of thepresent invention was 10% or less of the lesion area of non-treatedradish.

INDUSTRIAL APPLICABILITY

The plant diseases can be controlled by using the compound of thepresent invention.

1. A pyridazine compound represented by formula (1):

wherein, R¹ represents a chlorine atom, a bromine atom or a C1-C4 alkoxygroup; R² represents a C1-C4 alkyl group; R³ represents a halogen atom,a nitro group, a cyano group, a C1-C4 alkyl group optionally substitutedby at least one halogen atom, a C1-C4 alkoxy group optionallysubstituted by at least one halogen atom or a C1-C4 alkylthio groupoptionally substituted by at least one halogen atom; m represents aninteger of 0 to 5; provided that, when m represents an integer of 2 ormore, each of R³s is same or different; R⁴ a halogen atom, a nitrogroup, a cyano group, a C1-C4 alkyl group optionally substituted by atleast one halogen atom or a C1-C4 alkoxy group optionally substituted byat least one halogen atom; R⁵ represents a halogen atom, a nitro group,a cyano group, a C1-C4 alkyl group optionally substituted by at leastone halogen atom or a C1-C4 alkoxy group optionally substituted by atleast one halogen atom; n represents an integer of 0 to 4; providedthat, when n represents an integer of 2 or more, each of R⁵s is same ordifferent.
 2. The pyridazine compound according to claim 1, wherein m is1 or 2 and n is 0, 1 or 2 in the formula (1).
 3. The pyridazine compoundaccording to claim 1, wherein R¹ is a chlorine atom or a bromine atom,R² is a methyl group, and R⁴ is a halogen atom in the formula (1).
 4. Afungicidal composition comprising the pyridazine compound according toclaim 1 as an active ingredient and a carrier.
 5. A compound representedby formula (2):

wherein, R² represents a C1-C4 alkyl group; R³ represents a halogenatom, a nitro group, a cyano group, a C1-C4 alkyl group optionallysubstituted by at least one halogen atom, a C1-C4 alkoxy groupoptionally substituted by at least one halogen atom or a C1-C4 alkylthiogroup optionally substituted by at least one halogen atom m representsan integer of 0 to 5; provided that, when m represents an integer of 2or more, each of R³s is same or different; R⁴ represents a halogen atom,a nitro group, a cyano group, a C1-C4 alkyl group optionally substitutedby at least one halogen atom or a C1-C4 alkoxy group optionallysubstituted by at least one halogen atom; R⁵ represents a halogen atom,a nitro group, a cyano group, a C1-C4 alkyl group optionally substitutedby at least one halogen atom or a C1-C4 alkoxy group optionallysubstituted by at least one halogen atom; n represents an integer of 0to 4; provided that, when n represents an integer of 2 or more, each ofR⁵s is same or different.
 6. A compound represented by formula (1-3):

wherein, R¹ represents a chlorine atom, a bromine atom or a C1-C4 alkoxygroup; R² represents a C1-C4 alkyl group; R³⁻¹ represents a halogenatom, a cyano group, a C1-C4 alkyl group optionally substituted by atleast one halogen atom, a C1-C4 alkoxy group optionally substituted byat least one halogen atom or a C1-C4 alkylthio group optionallysubstituted by at least one halogen atom; m represents an integer of 0to 5; provided that, when m represents an integer of 2 or more, each ofR³⁻¹s is same or different.